U.S. patent number 7,964,746 [Application Number 12/058,751] was granted by the patent office on 2011-06-21 for copper precursors for cvd/ald/digital cvd of copper metal films.
This patent grant is currently assigned to Advanced Technology Materials, Inc.. Invention is credited to Thomas H. Baum, Tianniu Chen, Juan E. Dominguez, Bryan C. Hendrix, Adrien R. Lavoie, Jeffrey F. Roeder, Harsono S. Simka, Chongying Xu.
United States Patent |
7,964,746 |
Chen , et al. |
June 21, 2011 |
**Please see images for:
( Certificate of Correction ) ** |
Copper precursors for CVD/ALD/digital CVD of copper metal films
Abstract
Copper precursors useful for depositing copper or
copper-containing films on substrates, e.g., microelectronic device
substrates or other surfaces. The precursors includes copper
compounds of various classes, including copper borohydrides, copper
compounds with cyclopentadienyl-type ligands, copper compounds with
cyclopentadienyl-type and isocyanide ligands, and stabilized copper
hydrides. The precursors can be utilized in solid or liquid forms
that are volatilized to form precursor vapor for contacting with
the substrate, to form deposited copper by techniques such as
chemical vapor deposition (CVD), atomic layer deposition (ALD) or
rapid vapor deposition (digital CVD).
Inventors: |
Chen; Tianniu (Rocky Hill,
CT), Xu; Chongying (New Milford, CT), Baum; Thomas H.
(New Fairfield, CT), Hendrix; Bryan C. (Danbury, CT),
Roeder; Jeffrey F. (Brookfield, CT), Dominguez; Juan E.
(Hillsboro, OR), Lavoie; Adrien R. (Beaverton, OR),
Simka; Harsono S. (Saratoga, CA) |
Assignee: |
Advanced Technology Materials,
Inc. (Danbury, CT)
|
Family
ID: |
39795539 |
Appl.
No.: |
12/058,751 |
Filed: |
March 30, 2008 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20080242880 A1 |
Oct 2, 2008 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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60908998 |
Mar 30, 2007 |
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Current U.S.
Class: |
556/112; 548/402;
556/8; 118/726; 549/3; 556/9; 106/1.26; 549/206 |
Current CPC
Class: |
C07F
17/00 (20130101); C23C 16/45553 (20130101) |
Current International
Class: |
C07F
1/08 (20060101); C23C 18/40 (20060101) |
Field of
Search: |
;556/8,9,112 ;118/726
;106/1.26 ;549/3,206 ;548/402 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
Macomber et al., Journal of American Chemical Society, vol. 105,
No. 16, pp. 5325-5329 (1983). cited by examiner .
Anderson et al., Organometallics, vol. 17, No. 22, pp. 4917-4920
(1998). cited by examiner .
Artaud-Gillet et al., Journal of Crystal Growth, vol. 248, pp.
163-168 (2003). cited by examiner .
Ren et al., Journal of Organometallic chemistry, vol. 691, pp.
4109-4113 (available in the Web Jun. 21, 2006). cited by examiner
.
Li, Wentao, et al., "Additives for stabilizing LiPF6-based
electrolyes against thermal decomposition", "J. Electrochem. Soc.",
2005, pp. A1361-A1365, vol. 152, No. 7. cited by other .
Oakley, Sarah H., et al., "Structural consequences of the
prohibition of hydrogen bonding in copper-guanidine systems",
"Inorg. Chem.", 2004, pp. 5168-5172, vol. 43, No. 16. cited by
other.
|
Primary Examiner: Gonzalez; Porfirio Nazario
Attorney, Agent or Firm: Hultquist; Steven J. Hulquist IP
Chappuis; Margaret
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATION
The benefit of U.S. Provisional Patent Application 60/908,998 filed
Mar. 30, 2007 in the names of Tianniu Chen, et al. for "COPPER
PRECURSORS FOR CVD/ALD/DIGITAL CVD OF COPPER METAL FILMS" is hereby
claimed under the provisions of 35 USC 119. The disclosure of said
U.S. Provisional Patent Application 60/908,998 is hereby
incorporated herein by reference, in its entirety, for all
purposes.
Claims
What is claimed is:
1. A copper precursor composition comprising: a compound selected
from the group consisting of compounds of formulae (i)-(viii):
##STR00083## wherein each of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and
R.sup.5 may be the same as or different from the others, and each
is independently selected from among hydrogen, C.sub.1-C.sub.6
alkyl, C.sub.3-C.sub.6 alkenyl, C.sub.6-C.sub.10 aryl,
C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6
amino, hydrazino of the formula R.sub.aR.sub.bNNR.sub.c-- wherein
each of R.sub.a, R.sub.b and R.sub.a may be the same as or
different from one another and each is independently selected from
among C.sub.1-C.sub.6 alkyl, and pendant ligands including
functional group(s) providing further coordination to the metal
center, selected from the group consisting of aminoalkyl,
alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, and groups
of the following formulae: ##STR00084## wherein each of
R.sub.1-R.sub.4 is the same as or different from one another, with
each being independently selected from among hydrogen and
C.sub.1-C.sub.6 straight chain or branched alkyl, C.sub.1-C.sub.6
straight chain or branched alkoxy, C.sub.6-C.sub.10 aryl and
NR.sub.5R.sub.6; each of R.sub.5 and R.sub.6 is the same as or
different from the other, with each being independently selected
from among C.sub.1-C.sub.6 straight chain or branched alkyl and
C.sub.6-C.sub.10 aryl; n and m are each selected independently from
0 to 4 with the proviso that m and n cannot be 0 at the same time,
and x is selected from 1 to 5; ##STR00085## wherein each of
R.sub.1-R.sub.4 is the same as or different from one another, with
each being independently selected from among hydrogen,
C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10 aryl; R.sub.5 is
selected from among C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; and n and m are selected independently from 0 to 4, with the
proviso that m and n cannot be 0 at the same time; each L may be
the same as or different from the other, each is a unidentate or
multidentate Lewis-base ligand, and each is independently selected
from the group consisting of phosphines, tertiary phosphines,
ethers, polyethers, amines, alkylamines, polyamines, glymes, crown
ethers, crown thioethers, cyclic polyamines (cyclenes), thioglymes,
C.sub.2-C.sub.6 alkynes, azoles, imidazoles, C.sub.2-C.sub.6
alkenes, pyridines, bipyridines, isonitriles, carbenes and
hetero-carbenes; ##STR00086## wherein each of R.sup.1, R.sup.2,
R.sup.3, R.sup.4 and R.sup.5 may be the same as or different from
the others, and each is independently selected from among hydrogen,
C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkenyl, C.sub.6-C.sub.10
aryl, C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6 alkylsilyl,
C.sub.1-C.sub.6 amino, hydrazino of the formula
R.sub.aR.sub.bNNR.sub.c-- wherein each of R.sub.a, R.sub.b and
R.sub.c may be the same as or different from one another and each
is independently selected from among C.sub.1-C.sub.6 alkyl, and
pendant ligands including functional group(s) providing further
coordination to the metal center, selected from the group
consisting of aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl,
and acetylalkyl, and groups of the following formulae: ##STR00087##
wherein each of R.sub.1-R.sub.4 is the same as or different from
one another, with each being independently selected from among
hydrogen and C.sub.1-C.sub.6 straight chain or branched alkyl,
C.sub.1-C.sub.6 straight chain or branched alkoxy, C.sub.6-C.sub.10
aryl and NR.sub.5R.sub.6; each of R.sub.5 and R.sub.6 is the same
as or different from the other, with each being independently
selected from among C.sub.1-C.sub.6 straight chain or branched
alkyl and C.sub.6-C.sub.10 aryl; n and m are each selected
independently from 0 to 4 with the proviso that m and n cannot be 0
at the same time, and x is selected from 1 to 5; ##STR00088##
wherein each of R.sub.1-R.sub.4 is the same as or different from
one another, with each being independently selected from among
hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10 aryl; R.sub.5
is selected from among C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; and n and m are selected independently from 0 to 4, with the
proviso that m and n cannot be 0 at the same time; ##STR00089##
wherein each of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 may
be the same as or different from the others, and each is
independently selected from among hydrogen, C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 alkenyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.6
alkoxy, C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6 amino,
hydrazino of the formula R.sub.aR.sub.bNNR.sub.c-- wherein each of
R.sub.a, R.sub.b and R.sub.c may be the same as or different from
one another and each is independently selected from among
C.sub.1-C.sub.6 alkyl, and pendant ligands including functional
group(s) providing further coordination to the metal center,
selected from the group consisting of aminoalkyl, alkoxyalkyl,
aryloxyalkyl, imidoalkyl, and acetylalkyl, and groups of the
following formulae: ##STR00090## wherein each of R.sub.1-R.sub.4 is
the same as or different from one another, with each being
independently selected from among hydrogen and C.sub.1-C.sub.6
straight chain or branched alkyl, C.sub.1-C.sub.6 straight chain or
branched alkoxy, C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of
R.sub.5 and R.sub.6 is the same as or different from the other,
with each being independently selected from among C.sub.1-C.sub.6
straight chain or branched alkyl and C.sub.6-C.sub.10 aryl; n and m
are each selected independently from 0 to 4 with the proviso that m
and n cannot be 0 at the same time, and x is selected from 1 to 5;
##STR00091## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same time;
each L may be the same as or different from the other, each is a
unidentate or multidentate Lewis-base ligand, and each is
independently selected from the group consisting of phosphines,
tertiary phosphines, ethers, polyethers, amines, alkylamines,
polyamines, glymes, crown ethers, crown thioethers, cyclic
polyamines (cyclenes), thioglymes, C.sub.2-C.sub.6 alkynes, azoles,
imidazoles, C.sub.2-C.sub.6 alkenes, pyridines, bipyridines,
isonitriles, carbenes and hetero-carbenes; ##STR00092## wherein
each of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 may be the
same as or different from the others, and each is independently
selected from among hydrogen, C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 alkenyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.6
alkoxy, C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6 amino,
hydrazino of the formula R.sub.aR.sub.bNNR.sub.c-- wherein each of
R.sub.a, R.sub.b and R.sub.c may be the same as or different from
one another and each is independently selected from among
C.sub.1-C.sub.6 alkyl, and pendant ligands including functional
group(s) providing further coordination to the metal center,
selected from the group consisting of aminoalkyl, alkoxyalkyl,
aryloxyalkyl, imidoalkyl, and acetylalkyl, and groups of the
following formulae: ##STR00093## wherein each of R.sub.1-R.sub.4 is
the same as or different from one another, with each being
independently selected from among hydrogen and C.sub.1-C.sub.6
straight chain or branched alkyl, C.sub.1-C.sub.6 straight chain or
branched alkoxy, C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of
R.sub.5 and R.sub.6 is the same as or different from the other,
with each being independently selected from among C.sub.1-C.sub.6
straight chain or branched alkyl and C.sub.6-C.sub.10 aryl; n and m
are each selected independently from 0 to 4 with the proviso that m
and n cannot be 0 at the same time, and x is selected from 1 to 5;
##STR00094## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same time;
##STR00095## wherein each of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and
R.sup.5 may be the same as or different from the others, and each
is independently selected from among hydrogen, C.sub.1-C.sub.6
alkyl, C.sub.1-C.sub.6 alkenyl, C.sub.6-C.sub.10 aryl,
C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6
amino, hydrazino of the formula R.sub.aR.sub.bNNR.sub.c-- wherein
each of R.sub.a, R.sub.b and R.sub.c may be the same as or
different from one another and each is independently selected from
among C.sub.1-C.sub.6 alkyl, and pendant ligands including
functional group(s) providing further coordination to the metal
center, selected from the group consisting of aminoalkyl,
alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, and groups
of the following formulae: ##STR00096## wherein each of
R.sub.1-R.sub.4 is the same as or different from one another, with
each being independently selected from among hydrogen and
C.sub.1-C.sub.6 straight chain or branched alkyl, C.sub.1-C.sub.6
straight chain or branched alkoxy, C.sub.6-C.sub.10 aryl and
NR.sub.5R.sub.6; each of R.sub.5 and R.sub.6 is the same as or
different from the other, with each being independently selected
from among C.sub.1-C.sub.6 straight chain or branched alkyl and
C.sub.6-C.sub.10 aryl; n and m are each selected independently from
0 to 4 with the proviso that m and n cannot be 0 at the same time,
and x is selected from 1 to 5; ##STR00097## wherein each of
R.sub.1-R.sub.4 is the same as or different from one another, with
each being independently selected from among hydrogen,
C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10 aryl; R.sub.5 is
selected from among C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; and n and m are selected independently from 0 to 4, with the
proviso that m and n cannot be 0 at the same time; each L may be
the same as or different from the other, each is a unidentate or
multidentate Lewis-base ligand, and each is independently selected
from the group consisting of phosphines, tertiary phosphines,
ethers, polyethers, amines, alkylamines, polyamines, glymes, crown
ethers, crown thioethers, cyclic polyamines (cyclenes), thioglymes,
C.sub.2-C.sub.6 alkynes, azoles, imidazoles, C.sub.2-C.sub.6
alkenes, pyridines, bipyridines, isonitriles, carbenes and
hetero-carbenes; ##STR00098## wherein each of R.sup.1, R.sup.2,
R.sup.3, R.sup.4 and R.sup.5 may be the same as or different from
the others, and each is independently selected from among hydrogen,
C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkenyl, C.sub.6-C.sub.10
aryl, C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6 alkylsilyl,
C.sub.1-C.sub.6 amino, hydrazino of the formula
R.sub.aR.sub.bNNR.sub.c-- wherein each of R.sub.a, R.sub.b and
R.sub.c may be the same as or different from one another and each
is independently selected from among C.sub.1-C.sub.6 alkyl, and
pendant ligands including functional group(s) providing further
coordination to the metal center, selected from the group
consisting of aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl,
and acetylalkyl, and groups of the following formulae: ##STR00099##
wherein each of R.sub.1-R.sub.4 is the same as or different from
one another, with each being independently selected from among
hydrogen and C.sub.1-C.sub.6 straight chain or branched alkyl,
C.sub.1-C.sub.6 straight chain or branched alkoxy, C.sub.6-C.sub.10
aryl and NR.sub.5R.sub.6; each of R.sub.5 and R.sub.6 is the same
as or different from the other, with each being independently
selected from among C.sub.1-C.sub.6 straight chain or branched
alkyl and C.sub.6-C.sub.10 aryl; n and m are each selected
independently from 0 to 4 with the proviso that m and n cannot be 0
at the same time, and x is selected from 1 to 5; ##STR00100##
wherein each of R.sub.1-R.sub.4 is the same as or different from
one another, with each being independently selected from among
hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10 aryl; R.sub.5
is selected from among C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; and n and m are selected independently from 0 to 4, with the
proviso that m and n cannot be 0 at the same time; ##STR00101##
wherein each of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 may
be the same as or different from the others, and each is
independently selected from among hydrogen, C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 alkenyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.6
alkoxy, C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6 amino,
hydrazino of the formula R.sub.aR.sub.bNNR.sub.c-- wherein each of
R.sub.a, R.sub.b and R.sub.c may be the same as or different from
one another and each is independently selected from among
C.sub.1-C.sub.6 alkyl, and pendant ligands including functional
group(s) providing further coordination to the metal center,
selected from the group consisting of aminoalkyl, alkoxyalkyl,
aryloxyalkyl, imidoalkyl, and acetylalkyl, and groups of the
following formulae: ##STR00102## wherein each of R.sub.1-R.sub.4 is
the same as or different from one another, with each being
independently selected from among hydrogen and C.sub.1-C.sub.6
straight chain or branched alkyl, C.sub.1-C.sub.6 straight chain or
branched alkoxy, C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of
R.sub.5 and R.sub.6 is the same as or different from the other,
with each being independently selected from among C.sub.1-C.sub.6
straight chain or branched alkyl and C.sub.6-C.sub.10 aryl; n and m
are each selected independently from 0 to 4 with the proviso that m
and n cannot be 0 at the same time, and x is selected from 1 to 5;
##STR00103## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same time;
L is a unidentate or multidentate Lewis-base ligand selected from
the group consisting of phosphines, tertiary phosphines, ethers,
polyethers, amines, alkylamines, polyamines, glymes, crown ethers,
crown thioethers, cyclic polyamines (cyclenes), thioglymes,
C.sub.2-C.sub.6 alkynes, azoles, imidazoles, C.sub.2-C.sub.6
alkenes, pyridines, bipyridines, isonitriles, carbenes and
hetero-carbenes; ##STR00104## wherein each of R.sup.1, R.sup.2,
R.sup.3, R.sup.4 and R.sup.5 may be the same as or different from
the others, and each is independently selected from among hydrogen,
C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkenyl, C.sub.6-C.sub.10
aryl, C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6 alkylsilyl,
C.sub.1-C.sub.6 amino, hydrazino of the formula
R.sub.aR.sub.bNNR.sub.c-- wherein each of R.sub.a, R.sub.b and
R.sub.c may be the same as or different from one another and each
is independently selected from among C.sub.1-C.sub.6 alkyl, and
pendant ligands including functional group(s) providing further
coordination to the metal center, selected from the group
consisting of aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl,
and acetylalkyl, and groups of the following formulae: ##STR00105##
wherein each of R.sub.1-R.sub.4 is the same as or different from
one another, with each being independently selected from among
hydrogen and C.sub.1-C.sub.6 straight chain or branched alkyl,
C.sub.1-C.sub.6 straight chain or branched alkoxy, C.sub.6-C.sub.10
aryl and NR.sub.5R.sub.6; each of R.sub.5 and R.sub.6 is the same
as or different from the other, with each being independently
selected from among C.sub.1-C.sub.6 straight chain or branched
alkyl and C.sub.6-C.sub.10 aryl; n and m are each selected
independently from 0 to 4 with the proviso that m and n cannot be 0
at the same time, and x is selected from 1 to 5; ##STR00106##
wherein each of R.sub.1-R.sub.4 is the same as or different from
one another, with each being independently selected from among
hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10 aryl; R.sub.5
is selected from among C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; and n and m are selected independently from 0 to 4, with the
proviso that m and n cannot be 0 at the same time; and a solvent
medium.
2. The copper precursor formulation of claim 1, wherein the solvent
medium comprises a solvent selected from the group consisting of
alkane solvents, hexane, heptane, octane, pentane, aryl solvents,
benzene, toluene, amines, triethylamine, tert-butylamine, imines,
carbodiimides, N,N'-diisopropylcarbodiimide, alcohols, ethers,
ketones, aldehydes, amidines, guanadines, and isoureas.
3. A precursor vapor composition, comprising a vapor of a copper
precursor composition of claim 1.
4. A reagent source package, comprising a storage and dispensing
vessel containing a copper precursor composition of claim 1.
5. A method of making a cyclopentadienyl-type copper precursor,
comprising carrying out a synthesis process comprising a synthetic
route selected from the group consisting of: (I) the synthetic
route comprising ##STR00107## wherein L is a unidentate or
multidentate Lewis-base ligand selected from the group consisting
of phosphines, tertiary phosphines, ethers, polyethers, amines,
alkylamines, polyamines, glymes, crown ethers, crown thioethers,
cyclic polyamines (cyclenes), thioglymes, C.sub.2-C.sub.6 alkynes,
azoles, imidazoles, C.sub.2-C.sub.6 alkenes, pyridines,
bipyridines, isonitriles, carbenes and hetero-carbenes; and (II)
the synthetic route corresponding to synthetic route (I) wherein
cyclopentadienyl substituents instead of being all methyl are each
independently selected from among hydrogen, C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 alkenyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.6
alkoxy, C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6 amino,
hydrazino of the formula R.sub.aR.sub.bNNR.sub.c-- wherein each of
R.sub.a, R.sub.b and R.sub.c may be the same as or different from
one another and each is independently selected from among
C.sub.1-C.sub.6 alkyl, and pendant ligands including functional
group(s) providing further coordination to the metal center, such
as, for example, aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl,
and acetylalkyl, wherein suitable groups in these classes include
those of the following formulae: ##STR00108## wherein each of
R.sub.1-R.sub.4 is the same as or different from one another, with
each being independently selected from among hydrogen and
C.sub.1-C.sub.6 straight chain or branched alkyl, C.sub.1-C.sub.6
straight chain or branched alkoxy, C.sub.6-C.sub.10 aryl and
NR.sub.5R.sub.6; each of R.sub.5 and R.sub.6 is the same as or
different from the other, with each being independently selected
from among C.sub.1-C.sub.6 straight chain or branched alkyl and
C.sub.6-C.sub.10 aryl; n and m are each selected independently from
0 to 4 with the proviso that m and n cannot be 0 at the same time,
and x is selected from 1 to 5; ##STR00109## wherein each of
R.sub.1-R.sub.4 is the same as or different from one another, with
each being independently selected from among hydrogen,
C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10 aryl; R.sub.5 is
selected from among C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; and n and m are selected independently from 0 to 4, with the
proviso that m and n cannot be 0 at the same time; and with L being
a unidentate or multidentate Lewis-base ligand selected from the
group consisting of phosphines, tertiary phosphines, ethers,
polyethers, amines, alkylamines, polyamines, glymes, crown ethers,
crown thioethers, cyclic polyamines (cyclenes), thioglymes,
C.sub.2-C.sub.6 alkynes, azoles, imidazoles, C.sub.2-C.sub.6
alkenes, pyridines, bipyridines, isonitriles, carbenes and
hetero-carbenes; and recovering said cyclopentadienyl-type copper
precursor from a reaction volume including reactants and products
of said synthesis.
6. A copper precursor compound selected from the group consisting
of CpCu(CyNC), EtCpCu(tBuNC), and MeCpCu(tBuNC), wherein Cp is
cyclopentadienyl, Cy is cyclohexyl, Et is ethyl, and tBu is
tertiary butyl.
7. The copper precursor compound of claim 6, comprising
CpCu(CyNC).
8. The copper precursor compound of claim 6, comprising
EtCpCu(tBuNC).
9. The copper precursor compound of claim 6, comprising
MeCpCu(tBuNC).
10. A copper precursor formulation comprising a copper precursor
compound of claim 6 and a solvent medium.
11. The copper precursor formulation of claim 10, wherein the
solvent medium comprises a solvent selected from the group
consisting of alkane solvents, hexane, heptane, octane, pentane,
aryl solvents, benzene, toluene, amines, triethylamine,
tert-butylamine, imines, carbodiimides,
N,N'-diisopropylcarbodiimide, alcohols, ethers, ketones, aldehydes,
amidines, guanadines, and isoureas.
12. A precursor vapor composition, comprising a vapor of a copper
precursor compound of claim 6.
13. A reagent source package, comprising a storage and dispensing
vessel containing a copper precursor compound of claim 6.
14. A copper precursor compound selected from the group consisting
of compounds of formulae (i)-(viii): ##STR00110## wherein each of
R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 may be the same as
or different from the others, and each is independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6
alkenyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.6 alkoxy,
C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6 amino, hydrazino of the
formula R.sub.aR.sub.bNNR.sub.c-- wherein each of R.sub.a, R.sub.b
and R.sub.c may be the same as or different from one another and
each is independently selected from among C.sub.1-C.sub.6 alkyl,
and pendant ligands including functional group(s) providing further
coordination to the metal center, selected from the group
consisting of aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl,
and acetylalkyl, and groups of the following formulae: ##STR00111##
wherein each of R.sub.1-R.sub.4 is the same as or different from
one another, with each being independently selected from among
hydrogen and C.sub.1-C.sub.6 straight chain or branched alkyl,
C.sub.1-C.sub.6 straight chain or branched alkoxy, C.sub.6-C.sub.10
aryl and NR.sub.5R.sub.6; each of R.sub.5 and R.sub.6 is the same
as or different from the other, with each being independently
selected from among C.sub.1-C.sub.6 straight chain or branched
alkyl and C.sub.6-C.sub.10 aryl; n and m are each selected
independently from 0 to 4 with the proviso that m and n cannot be 0
at the same time, and x is selected from 1 to 5; ##STR00112##
wherein each of R.sub.1-R.sub.4 is the same as or different from
one another, with each being independently selected from among
hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10 aryl; R.sub.5
is selected from among C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; and n and m are selected independently from 0 to 4, with the
proviso that m and n cannot be 0 at the same time; each L may be
the same as or different from the other, each is a unidentate or
multidentate Lewis-base ligand, and each is independently selected
from the group consisting of ethers, polyethers, amines,
alkylamines, polyamines, glymes, crown ethers, crown thioethers,
cyclic polyamines (cyclenes), thioglymes, C.sub.2-C.sub.6 alkynes,
azoles, imidazoles, pyridines, bipyridines, and isonitriles;
##STR00113## wherein each of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and
R.sup.5 may be the same as or different from the others, and each
is independently selected from among C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 alkenyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.6
alkoxy, C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6 amino,
hydrazino of the formula R.sub.aR.sub.bNNR.sub.c-- wherein each of
R.sub.a, R.sub.b and R.sub.c may be the same as or different from
one another and each is independently selected from among
C.sub.1-C.sub.6 alkyl, and pendant ligands including functional
group(s) providing further coordination to the metal center,
selected from the group consisting of aminoalkyl, alkoxyalkyl,
aryloxyalkyl, imidoalkyl, and acetylalkyl, and groups of the
following formulae: ##STR00114## wherein each of R.sub.1-R.sub.4 is
the same as or different from one another, with each being
independently selected from among hydrogen and C.sub.1-C.sub.6
straight chain or branched alkyl, C.sub.1-C.sub.6 straight chain or
branched alkoxy, C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of
R.sub.5 and R.sub.6 is the same as or different from the other,
with each being independently selected from among C.sub.1-C.sub.6
straight chain or branched alkyl and C.sub.6-C.sub.10 aryl; n and m
are each selected independently from 0 to 4 with the proviso that m
and n cannot be 0 at the same time, and x is selected from 1 to 5;
##STR00115## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same time;
##STR00116## wherein each of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and
R.sup.5 may be the same as or different from the others, and each
is independently selected from among hydrogen, C.sub.1-C.sub.6
alkyl, C.sub.1-C.sub.6 alkenyl, C.sub.6-C.sub.10 aryl,
C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6
amino, hydrazino of the formula R.sub.aR.sub.bNNR.sub.c-- wherein
each of R.sub.a, R.sub.b and R.sub.c may be the same as or
different from one another and each is independently selected from
among C.sub.1-C.sub.6 alkyl, and pendant ligands including
functional group(s) providing further coordination to the metal
center, selected from the group consisting of aminoalkyl,
alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, and groups
of the following formulae: ##STR00117## wherein each of
R.sub.1-R.sub.4 is the same as or different from one another, with
each being independently selected from among hydrogen and
C.sub.1-C.sub.6 straight chain or branched alkyl, C.sub.1-C.sub.6
straight chain or branched alkoxy, C.sub.6-C.sub.10 aryl and
NR.sub.5R.sub.6; each of R.sub.5 and R.sub.6 is the same as or
different from the other, with each being independently selected
from among C.sub.1-C.sub.6 straight chain or branched alkyl and
C.sub.6-C.sub.10 aryl; n and m are each selected independently from
0 to 4 with the proviso that m and n cannot be 0 at the same time,
and x is selected from 1 to 5; ##STR00118## wherein each of
R.sub.1-R.sub.4 is the same as or different from one another, with
each being independently selected from among hydrogen,
C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10 aryl; R.sub.5 is
selected from among C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; and n and m are selected independently from 0 to 4, with the
proviso that m and n cannot be 0 at the same time; each L may be
the same as or different from the other, each is a unidentate or
multidentate Lewis-base ligand, and each is independently selected
from the group consisting of ethers, polyethers, amines,
alkylamines, polyamines, glymes, crown ethers, crown thioethers,
cyclic polyamines (cyclenes), thioglymes, C.sub.2-C.sub.6 alkynes,
azoles, imidazoles, pyridines, bipyridines, and isonitriles;
##STR00119## wherein each of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and
R.sup.5 may be the same as or different from the others, and each
is independently selected from among hydrogen, C.sub.1-C.sub.6
alkyl, C.sub.1-C.sub.6 alkenyl, C.sub.6-C.sub.10 aryl,
C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6
amino, hydrazino of the formula R.sub.aR.sub.bNNR.sub.c-- wherein
each of R.sub.a, R.sub.b and R.sub.c may be the same as or
different from one another and each is independently selected from
among C.sub.1-C.sub.6 alkyl, and pendant ligands including
functional group(s) providing further coordination to the metal
center, selected from the group consisting of aminoalkyl,
alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, and groups
of the following formulae: ##STR00120## wherein each of
R.sub.1-R.sub.4 is the same as or different from one another, with
each being independently selected from among hydrogen and
C.sub.1-C.sub.6 straight chain or branched alkyl, C.sub.1-C.sub.6
straight chain or branched alkoxy, C.sub.6-C.sub.10 aryl and
NR.sub.5R.sub.6; each of R.sub.5 and R.sub.6 is the same as or
different from the other, with each being independently selected
from among C.sub.1-C.sub.6 straight chain or branched alkyl and
C.sub.6-C.sub.10 aryl; n and m are each selected independently from
0 to 4 with the proviso that m and n cannot be 0 at the same time,
and x is selected from 1 to 5; ##STR00121## wherein each of
R.sub.1-R.sub.4 is the same as or, different from one another, with
each being independently selected from among hydrogen,
C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10 aryl; R.sub.5 is
selected from among C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; and n and m are selected independently from 0 to 4, with the
proviso that m and n cannot be 0 at the same time; ##STR00122##
wherein each of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 may
be the same as or different from the others, and each is
independently selected from among hydrogen, C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 alkenyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.6
alkoxy, C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6 amino,
hydrazino of the formula R.sub.aR.sub.bNNR.sub.c-- wherein each of
R.sub.a, R.sub.b and R.sub.c may be the same as or different from
one another and each is independently selected from among
C.sub.1-C.sub.6 alkyl, and pendant ligands including functional
group(s) providing further coordination to the metal center,
selected from the group consisting of aminoalkyl, alkoxyalkyl,
aryloxyalkyl, imidoalkyl, and acetylalkyl, and groups of the
following formulae: ##STR00123## wherein each of R.sub.1-R.sub.4 is
the same as or different from one another, with each being
independently selected from among hydrogen and C.sub.1-C.sub.6
straight chain or branched alkyl, C.sub.1-C.sub.6 straight chain or
branched alkoxy, C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of
R.sub.5 and R.sub.6 is the same as or different from the other,
with each being independently selected from among C.sub.1-C.sub.6
straight chain or branched alkyl and C.sub.6-C.sub.10 aryl; n and m
are each selected independently from 0 to 4 with the proviso that m
and n cannot be 0 at the same time, and x is selected from 1 to 5;
##STR00124## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same time;
each L may be the same as or different from the other, each is a
unidentate or multidentate Lewis-base ligand, and each is
independently selected from the group consisting of phosphines,
tertiary phosphines, ethers, polyethers, amines, alkylamines,
polyamines, glymes, crown ethers, crown thioethers, cyclic
polyamines (cyclenes), thioglymes, C.sub.2-C.sub.6 alkynes, azoles,
imidazoles, C.sub.2-C.sub.6 alkenes, pyridines, bipyridines,
isonitriles, carbenes and hetero-carbenes; ##STR00125## wherein
each of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 may be the
same as or different from the others, and each is independently
selected from among hydrogen, C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 alkenyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.6
alkoxy, C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6 amino,
hydrazino of the formula R.sub.aR.sub.bNNR.sub.c-- wherein each of
R.sub.a, R.sub.b and R.sub.c may be the same as or different from
one another and each is independently selected from among
C.sub.1-C.sub.6 alkyl, and pendant ligands including functional
group(s) providing further coordination to the metal center,
selected from the group consisting of aminoalkyl, alkoxyalkyl,
aryloxyalkyl, imidoalkyl, and acetylalkyl, and groups of the
following formulae: ##STR00126## wherein each of R.sub.1-R.sub.4 is
the same as or different from one another, with each being
independently selected from among hydrogen and C.sub.1-C.sub.6
straight chain or branched alkyl, C.sub.1-C.sub.6 straight chain or
branched alkoxy, C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of
R.sub.5 and R.sub.6 is the same as or different from the other,
with each being independently selected from among C.sub.1-C.sub.6
straight chain or branched alkyl and C.sub.6-C.sub.10 aryl; n and m
are each selected independently from 0 to 4 with the proviso that m
and n cannot be 0 at the same time, and x is selected from 1 to 5;
##STR00127## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same time;
##STR00128## wherein each of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and
R.sup.5 may be the same as or different from the others, and each
is independently selected from among hydrogen, C.sub.1-C.sub.6
alkyl, C.sub.1-C.sub.6 alkenyl, C.sub.6-C.sub.10 aryl,
C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6
amino, hydrazino of the formula R.sub.aR.sub.bNNR.sub.c-- wherein
each of R.sub.a, R.sub.b and R.sub.c may be the same as or
different from one another and each is independently selected from
among C.sub.1-C.sub.6 alkyl, and pendant ligands including
functional group(s) providing further coordination to the metal
center, selected from the group consisting of aminoalkyl,
alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, and groups
of the following formulae: ##STR00129## wherein each of
R.sub.1-R.sub.4 is the same as or different from one another, with
each being independently selected from among hydrogen and
C.sub.1-C.sub.6 straight chain or branched alkyl, C.sub.1-C.sub.6
straight chain or branched alkoxy, C.sub.6-C.sub.10 aryl and
NR.sub.5R.sub.6; each of R.sub.5 and R.sub.6 is the same as or
different from the other, with each being independently selected
from among C.sub.1-C.sub.6 straight chain or branched alkyl and
C.sub.6-C.sub.10 aryl; n and m are each selected independently from
0 to 4 with the proviso that m and n cannot be 0 at the same time,
and x is selected from 1 to 5; ##STR00130## wherein each of
R.sub.1-R.sub.4 is the same as or different from one another, with
each being independently selected from among hydrogen,
C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10 aryl; R.sub.5 is
selected from among C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; and n and m are selected independently from 0 to 4, with the
proviso that m and n cannot be 0 at the same time; L is a
unidentate or multidentate Lewis-base ligand selected from the
group consisting of phosphines, tertiary phosphines, ethers,
polyethers, amines, alkylamines, polyamines, glymes, crown ethers,
crown thioethers, cyclic polyamines (cyclenes), thioglymes,
C.sub.2-C.sub.6 alkynes, azoles, imidazoles, C.sub.2-C.sub.6
alkenes, pyridines, bipyridines, isonitriles, carbenes and
hetero-carbenes; and ##STR00131## wherein each of R.sup.1, R.sup.2,
R.sup.3, R.sup.4 and R.sup.5 may be the same as or different from
the others, and each is independently selected from among hydrogen,
C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkenyl, C.sub.6-C.sub.10
aryl, C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6 alkylsilyl,
C.sub.1-C.sub.6 amino, hydrazino of the formula
R.sub.aR.sub.bNNR.sub.c-- wherein each of R.sub.a, R.sub.b and
R.sub.c may be the same as or different from one another and each
is independently selected from among C.sub.1-C.sub.6 alkyl, and
pendant ligands including functional group(s) providing further
coordination to the metal center, selected from the group
consisting of aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl,
and acetylalkyl, and groups of the following formulae: ##STR00132##
wherein each of R.sub.1-R.sub.4 is the same as or different from
one another, with each being independently selected from among
hydrogen and C.sub.1-C.sub.6 straight chain or branched alkyl,
C.sub.1-C.sub.6 straight chain or branched alkoxy, C.sub.6-C.sub.10
aryl and NR.sub.5R.sub.6; each of R.sub.5 and R.sub.6 is the same
as or different from the other, with each being independently
selected from among C.sub.1-C.sub.6 straight chain or branched
alkyl and C.sub.6-C.sub.10 aryl; n and m are each selected
independently from 0 to 4 with the proviso that m and n cannot be 0
at the same time, and x is selected from 1 to 5; ##STR00133##
wherein each of R.sub.1-R.sub.4 is the same as or different from
one another, with each being independently selected from among
hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10 aryl; R.sub.5
is selected from among C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; and n and m are selected independently from 0 to 4, with the
proviso that m and n cannot be 0 at the same time.
Description
FIELD OF THE INVENTION
The present invention relates to copper precursors useful for
deposition of copper, e.g., on a microelectronic device substrate,
as well as to corresponding deposition methods utilizing such
precursors, and to microelectronic device structures and products
formed by use of such copper precursors and deposition methods.
DESCRIPTION OF THE RELATED ART
As a result of its low resistivity, low contact resistance, and
ability to enhance device performance through the reduction of RC
time delays, copper has emerged as a preferred metal for
metallization of very large scale integrated (VLSI) devices. Copper
metallization has been adopted by many microelectronic device
manufacturers for production of microelectronic chips, thin-film
recording heads and packaging components.
Two primary factors--the lower resistivity and the increased
electromigration resistance that copper offers relative to aluminum
have rapidly accelerated the conversion from aluminum to copper
interconnects in IC chips manufacturing. This transition has
resulted in the introduction of many new processes and materials,
but at the same time has posed significant challenges to the
microelectronics manufacturing industry. The deposition of the
copper thin films at the lower interconnect level is one of the
major challenges. As the dimensions shrink, it becomes increasingly
difficult to sputter-deposit pinhole-free copper seed layers for
electrodeposition of copper. In this circumstance, CVD/ALD of
copper as a seed layer for electrodeposition or for the fill of the
finest features becomes attractive.
Chemical vapor deposition (CVD) of copper provides uniform coverage
for the metallization. Atomic layer deposition (ALD), which is a
modified CVD process, also provides uniform step coverage which is
critical for copper seed layers. In ALD an excess amount of
precursor is delivered to the deposition chamber for reaction
therein to form a monolayer of reacted precursor on the wafer
surface. The deposition chamber is purged with a carrier gas to
remove unreacted precursor followed by the delivery of a reactant
to the deposition chamber for reaction with the monolayer of
reacted precursor to form the preferred material. This cycle is
repeated until the desired thickness of material is achieved.
Advantageously, ALD provides uniform step coverage and a high level
of control over film thicknesses and as such is used extensively
for the deposition of very thin films, such as diffusion barrier
layers and copper seed layers, on wafer surfaces having high aspect
ratio trenches and vias.
In an illustrative ALD process, sequential precursor pulses are
used to form a film, layer by layer. A first precursor may be
introduced to form a monolayer on a substrate, followed by
introduction of a second precursor to react with the monolayer to
form a first film layer. Each cycle including first and second
precursor pulses therefore forms one monolayer. The process then is
repeated to form successive layers until a film of desired
thickness is obtained.
Digital CVD, sometimes referred to as rapid vapor deposition (RVD)
is similar in nature to atomic layer deposition, involving
alternate introduction of reactant gases to the substrate but
without the restriction to a monolayer coverage of precursor in
each cycle. Many structures can be conformally covered using a
digital CVD approach with the advantage of providing faster film
formation than ALD.
Liquid precursors and/or solid precursors dissolved in suitable
solvents enable the direct injection and/or liquid delivery of
precursors into a CVD, ALD or digital CVD vaporizer unit. The
accurate and precise delivery rate can be obtained through
volumetric metering to achieve reproducibility during CVD, ALD or
digital CVD metallization of a VLSI device. Solid precursor
delivery via specially-designed devices, such as ATMI's ProE Vap
(ATMI, Danbury, Conn., USA) enables highly efficient transport of
solid precursors to a CVD or ALD reactor.
Copper beta-diketonate complexes have been thoroughly investigated
for use as CVD/ALD precursors, especially with fluorinated
beta-diketonate ligands. These precursors can be used to deposit
highly conductive, conformal films of copper. Nonetheless, when
such films are integrated with Ta or TaN surfaces of the barrier
material, weak adhesion is a consequence of fluorine contamination.
There is therefore a need for new precursors that are free of such
deficiency, without any halogengen constituents or other species
that could cause poor adhesion and/or otherwise increase contact
resistance with barrier materials. Accordingly, new precursors are
sought, which preferably have no halogengen atoms, and as few
heteroatoms (e.g., O, P, N, S) as possible.
SUMMARY OF THE INVENTION
The present invention relates to copper precursors useful in the
deposition of copper and copper-containing materials, e.g., on
microelectronic device substrates by techniques such as chemical
vapor deposition (CVD), atomic layer deposition (ALD) and digital
CVD, and to precursor formulations containing such precursors.
In one aspect, the invention relates to a copper precursor compound
selected from the group consisting of compounds of formulae
(i)-(xvii):
##STR00001## wherein each L may be the same as or different from
the other, each is a unidentate or multidentate Lewis-base ligand,
and each is independently selected from the group consisting of
phosphines, tertiary phosphines, ethers, polyethers, amines,
alkylamines, polyamines, glymes, crown ethers, crown thioethers,
cyclic polyamines (cyclenes), thioglymes, C.sub.2-C.sub.6 alkynes,
azoles, imidazoles, C.sub.2-C.sub.6 alkenes, pyridines,
bipyridines, isonitriles, carbenes and hetero-carbenes;
##STR00002## wherein each L may be the same as or different from
the other, each is a unidentate or multidentate Lewis-base ligand,
and each is independently selected from the group consisting of
phosphines, tertiary phosphines, ethers, polyethers, amines,
alkylamines, polyamines, glymes, crown ethers, crown thioethers,
cyclic polyamines (cyclenes), thioglymes, C.sub.2-C.sub.6 alkynes,
azoles, imidazoles, C.sub.2-C.sub.6 alkenes, pyridines,
bipyridines, isonitriles, carbenes and hetero-carbenes;
##STR00003## wherein each L may be the same as or different from
the other, each is a unidentate or multidentate Lewis-base ligand,
and each is independently selected from the group consisting of
phosphines, tertiary phosphines, ethers, polyethers, amines,
alkylamines, polyamines, glymes, crown ethers, crown thioethers,
cyclic polyamines (cyclenes), thioglymes, C.sub.2-C.sub.6 alkynes,
azoles, imidazoles, C.sub.2-C.sub.6 alkenes, pyridines,
bipyridines, isonitriles, carbenes and hetero-carbenes;
##STR00004## wherein each L may be the same as or different from
the other, each is a unidentate or multidentate Lewis-base ligand,
and each is independently selected from the group consisting of
phosphines, tertiary phosphines, ethers, polyethers, amines,
alkylamines, polyamines, glymes, crown ethers, crown thioethers,
cyclic polyamines (cyclenes), thioglymes, C.sub.2-C.sub.6 alkynes,
azoles, imidazoles, C.sub.2-C.sub.6 alkenes, pyridines,
bipyridines, isonitriles, carbenes and hetero-carbenes;
##STR00005## wherein each of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and
R.sup.5 may be the same as or different from the others, and each
is independently selected from among hydrogen, C.sub.1-C.sub.6
alkyl, C.sub.2-C.sub.6 alkenyl, C.sub.6-C.sub.10 aryl,
C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6
alkylamino, hydrazino of the formula R.sub.aR.sub.bNNR.sub.c--
wherein each of R.sub.a, R.sub.b and R.sub.c may be the same as or
different from one another and each is independently selected from
among C.sub.1-C.sub.6 alkyl, and pendant ligands including
functional group(s) providing further coordination to the metal
center, such as, for example, aminoalkyl, alkoxyalkyl,
aryloxyalkyl, imidoalkyl, and acetylalkyl, wherein suitable groups
in these classes include those of the following formulae:
##STR00006## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen and C.sub.1-C.sub.6 straight chain or branched
alkyl, C.sub.1-C.sub.6 straight chain or branched alkoxy,
C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of R.sub.5 and
R.sub.6 is the same as or different from the other, with each being
independently selected from among C.sub.1-C.sub.6 straight chain or
branched alkyl and C.sub.6-C.sub.10 aryl; n and m are each selected
independently from 0 to 4 with the proviso that m and n cannot be 0
at the same time, and x is selected from 1 to 5;
##STR00007## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same time;
each L may be the same as or different from the other, each is a
unidentate or multidentate Lewis-base ligand, and each is
independently selected from the group consisting of phosphines,
tertiary phosphines, ethers, polyethers, amines, alkylamines,
polyamines, glymes, crown ethers, crown thioethers, cyclic
polyamines (cyclenes), thioglymes, C.sub.2-C.sub.6 alkynes, azoles,
imidazoles, C.sub.2-C.sub.6 alkenes, pyridines, bipyridines,
isonitriles, carbenes and hetero-carbenes;
##STR00008## wherein each of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and
R.sup.5 may be the same as or different from the others, and each
is independently selected from among hydrogen, C.sub.1-C.sub.6
alkyl, C.sub.2-C.sub.6 alkenyl, C.sub.6-C.sub.10 aryl,
C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6
alkylamino, hydrazino of the formula R.sub.aR.sub.bNNR.sub.c--
wherein each of R.sub.a, R.sub.b and R.sub.c may be the same as or
different from one another and each is independently selected from
among C.sub.1-C.sub.6 alkyl, and pendant ligands including
functional group(s) providing further coordination to the metal
center, such as, for example, aminoalkyl, alkoxyalkyl,
aryloxyalkyl, imidoalkyl, and acetylalkyl, wherein suitable groups
in these classes include those of the following formulae:
##STR00009## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen and C.sub.1-C.sub.6 straight chain or branched
alkyl, C.sub.1-C.sub.6 straight chain or branched alkoxy,
C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of R.sub.5 and
R.sub.6 is the same as or different from the other, with each being
independently selected from among C.sub.1-C.sub.6 straight chain or
branched alkyl and C.sub.6-C.sub.10 aryl; n and m are each selected
independently from 0 to 4 with the proviso that m and n cannot be 0
at the same time, and x is selected from 1 to 5;
##STR00010## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same time;
each L may be the same as or different from the other, each is a
unidentate or multidentate Lewis-base ligand, and each is
independently selected from the group consisting of phosphines,
tertiary phosphines, ethers, polyethers, amines, alkylamines,
polyamines, glymes, crown ethers, crown thioethers, cyclic
polyamines (cyclenes), thioglymes, C.sub.2-C.sub.6 alkynes, azoles,
imidazoles, C.sub.2-C.sub.6 alkenes, pyridines, bipyridines,
isonitriles, carbenes and hetero-carbenes;
##STR00011## wherein each of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and
R.sup.5 may be the same as or different from the others, and each
is independently selected from among hydrogen, C.sub.1-C.sub.6
alkyl, C.sub.2-C.sub.6 alkenyl, C.sub.6-C.sub.10 aryl,
C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6
alkylamino, hydrazino of the formula R.sub.aR.sub.bNNR.sub.c--
wherein each of R.sub.a, R.sub.b and R.sub.c may be the same as or
different from one another and each is independently selected from
among C.sub.1-C.sub.6 alkyl, and pendant ligands including
functional group(s) providing further coordination to the metal
center, such as, for example, aminoalkyl, alkoxyalkyl,
aryloxyalkyl, imidoalkyl, and acetylalkyl, wherein suitable groups
in these classes include those of the following formulae:
##STR00012## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen and C.sub.1-C.sub.6 straight chain or branched
alkyl, C.sub.1-C.sub.6 straight chain or branched alkoxy,
C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of R.sub.5 and
R.sub.6 is the same as or different from the other, with each being
independently selected from among C.sub.1-C.sub.6 straight chain or
branched alkyl and C.sub.6-C.sub.10 aryl; n and m are each selected
independently from 0 to 4 with the proviso that m and n cannot be 0
at the same time, and x is selected from 1 to 5;
##STR00013## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same time;
each L may be the same as or different from the other, each is a
unidentate or multidentate Lewis-base ligand, and each is
independently selected from the group consisting of phosphines,
tertiary phosphines, ethers, polyethers, amines, alkylamines,
polyamines, glymes, crown ethers, crown thioethers, cyclic
polyamines (cyclenes), thioglymes, C.sub.2-C.sub.6 alkynes, azoles,
imidazoles, C.sub.2-C.sub.6 alkenes, pyridines, bipyridines,
isonitriles, carbenes and hetero-carbenes;
##STR00014## wherein each of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and
R.sup.5 may be the same as or different from the others, and each
is independently selected from among hydrogen, C.sub.1-C.sub.6
alkyl, C.sub.2-C.sub.6 alkenyl, C.sub.6-C.sub.10 aryl,
C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6
alkylamino, hydrazino of the formula R.sub.aR.sub.bNNR.sub.c--
wherein each of R.sub.a, R.sub.b and R.sub.c may be the same as or
different from one another and each is independently selected from
among C.sub.1-C.sub.6 alkyl, and pendant ligands including
functional group(s) providing further coordination to the metal
center, such as, for example, aminoalkyl, alkoxyalkyl,
aryloxyalkyl, imidoalkyl, and acetylalkyl, wherein suitable groups
in these classes include those of the following formulae:
##STR00015## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen and C.sub.1-C.sub.6 straight chain or branched
alkyl, C.sub.1-C.sub.6 straight chain or branched alkoxy,
C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of R.sub.5 and
R.sub.6 is the same as or different from the other, with each being
independently selected from among C.sub.1-C.sub.6 straight chain or
branched alkyl and C.sub.6-C.sub.10 aryl; n and m are each selected
independently from 0 to 4 with the proviso that m and n cannot be 0
at the same time, and x is selected from 1 to 5;
##STR00016## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same
time;
##STR00017## hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.2-C.sub.6
alkenyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.6 alkoxy,
C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6 amino, hydrazino of the
formula R.sub.aR.sub.bNNR.sub.c-- wherein each of R.sub.a, R.sub.b
and R.sub.c may be the same as or different from one another and
each is independently selected from among C.sub.1-C.sub.6 alkyl,
and pendant ligands including functional group(s) providing further
coordination to the metal center, such as, for example, aminoalkyl,
alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, wherein
suitable groups in these classes include those of the following
formulae:
##STR00018## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen and C.sub.1-C.sub.6 straight chain or branched
alkyl, C.sub.1-C.sub.6 straight chain or branched alkoxy,
C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of R.sub.5 and
R.sub.6 is the same as or different from the other, with each being
independently selected from among C.sub.1-C.sub.6 straight chain or
branched alkyl and C.sub.6-C.sub.10 aryl; n and m are each selected
independently from 0 to 4 with the proviso that m and n cannot be 0
at the same time, and x is selected from 1 to 5;
##STR00019## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same time;
L is a unidentate or multidentate Lewis-base ligand selected from
among phosphines, tertiary phosphines, ethers, polyethers, amines,
alkylamines, polyamines, glymes, crown ethers, crown thioethers,
cyclic polyamines (cyclenes), thioglymes, C.sub.2-C.sub.6 alkynes,
azoles, imidazoles, C.sub.2-C.sub.6 alkenes, pyridines,
bipyridines, isonitriles, carbenes and hetero-carbenes;
##STR00020## wherein each of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and
R.sup.5 may be the same as or different from the others, and each
is independently selected from among hydrogen, C.sub.1-C.sub.6
alkyl, C.sub.2-C.sub.6 alkenyl, C.sub.6-C.sub.10 aryl,
C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6
alkylamino, hydrazino of the formula R.sub.aR.sub.bNNR.sub.c--
wherein each of R.sub.a, R.sub.b and R.sub.c may be the same as or
different from one another and each is independently selected from
among C.sub.1-C.sub.6 alkyl, and pendant ligands including
functional group(s) providing further coordination to the metal
center, such as, for example, aminoalkyl, alkoxyalkyl,
aryloxyalkyl, imidoalkyl, and acetylalkyl, wherein suitable groups
in these classes include those of the following formulae:
##STR00021## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen and C.sub.1-C.sub.6 straight chain or branched
alkyl, C.sub.1-C.sub.6 straight chain or branched alkoxy,
C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of R.sub.5 and
R.sub.6 is the same as or different from the other, with each being
independently selected from among C.sub.1-C.sub.6 straight chain or
branched alkyl and C.sub.6-C.sub.10 aryl; n and m are each selected
independently from 0 to 4 with the proviso that m and n cannot be 0
at the same time, and x is selected from 1 to 5;
##STR00022## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same
time;
##STR00023## wherein each of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and
R.sup.5 may be the same as or different from the others, and each
is independently selected from among hydrogen, C.sub.1-C.sub.6
alkyl, C.sub.2-C.sub.6 alkenyl, C.sub.6-C.sub.10 aryl,
C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6
amino, hydrazino of the formula R.sub.aR.sub.bNNR.sub.c-- wherein
each of R.sub.a, R.sub.b and R.sub.c may be the same as or
different from one another and each is independently selected from
among C.sub.1-C.sub.6 alkyl, and pendant ligands including
functional group(s) providing further coordination to the metal
center, such as, for example, aminoalkyl, alkoxyalkyl,
aryloxyalkyl, imidoalkyl, and acetylalkyl, wherein suitable groups
in these classes include those of the following formulae:
##STR00024## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen and C.sub.1-C.sub.6 straight chain or branched
alkyl, C.sub.1-C.sub.6 straight chain or branched alkoxy,
C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of R.sub.5 and
R.sub.6 is the same as or different from the other, with each being
independently selected from among C.sub.1-C.sub.6 straight chain or
branched alkyl and C.sub.6-C.sub.10 aryl; n and m are each selected
independently from 0 to 4 with the proviso that m and n cannot be 0
at the same time, and x is selected from 1 to 5;
##STR00025## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same time;
L is a unidentate or multidentate Lewis-base ligand selected from
among phosphines, tertiary phosphines, ethers, polyethers, amines,
alkylamines, polyamines, glymes, crown ethers, crown thioethers,
cyclic polyamines (cyclenes), thioglymes, C.sub.2-C.sub.6 alkynes,
azoles, imidazoles, C.sub.2-C.sub.6 alkenes, pyridines,
bipyridines, isonitriles, carbenes and hetero-carbenes;
##STR00026## wherein each of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and
R.sup.5 may be the same as or different from the others, and each
is independently selected from among hydrogen, C.sub.1-C.sub.6
alkyl, C.sub.1-C.sub.6 alkenyl, C.sub.6-C.sub.10 aryl,
C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6
amino, hydrazino of the formula R.sub.aR.sub.bNNR.sub.c-- wherein
each of R.sub.a, R.sub.b and R.sub.c may be the same as or
different from one another and each is independently selected from
among C.sub.1-C.sub.6 alkyl, and pendant ligands including
functional group(s) providing further coordination to the metal
center, such as, for example, aminoalkyl, alkoxyalkyl,
aryloxyalkyl, imidoalkyl, and acetylalkyl, wherein suitable groups
in these classes include those of the following formulae:
##STR00027## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen and C.sub.1-C.sub.6 straight chain or branched
alkyl, C.sub.1-C.sub.6 straight chain or branched alkoxy,
C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of R.sub.5 and
R.sub.6 is the same as or different from the other, with each being
independently selected from among C.sub.1-C.sub.6 straight chain or
branched alkyl and C.sub.6-C.sub.10 aryl; n and m are each selected
independently from 0 to 4 with the proviso that m and n cannot be 0
at the same time, and x is selected from 1 to 5;
##STR00028## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same
time;
##STR00029## hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6
alkenyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.6 alkoxy,
C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6 amino, hydrazino of the
formula R.sub.aR.sub.bNNR.sub.c-- wherein each of R.sub.a, R.sub.b
and R.sub.c may be the same as or different from one another and
each is independently selected from among C.sub.1-C.sub.6 alkyl,
and pendant ligands including functional group(s) providing further
coordination to the metal center, such as, for example, aminoalkyl,
alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, wherein
suitable groups in these classes include those of the following
formulae:
##STR00030## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen and C.sub.1-C.sub.6 straight chain or branched
alkyl, C.sub.1-C.sub.6 straight chain or branched alkoxy,
C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of R.sub.5 and
R.sub.6 is the same as or different from the other, with each being
independently selected from among C.sub.1-C.sub.6 straight chain or
branched alkyl and C.sub.6-C.sub.10 aryl; n and m are each selected
independently from 0 to 4 with the proviso that m and n cannot be 0
at the same time, and x is selected from 1 to 5;
##STR00031## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same time;
L is a unidentate or multidentate Lewis-base ligand selected from
among phosphines, tertiary phosphines, ethers, polyethers, amines,
alkylamines, polyamines, glymes, crown ethers, crown thioethers,
cyclic polyamines (cyclenes), thioglymes, C.sub.2-C.sub.6 alkynes,
azoles, imidazoles, C.sub.2-C.sub.6 alkenes, pyridines,
bipyridines, isonitriles, carbenes and hetero-carbenes;
##STR00032## wherein each of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and
R.sup.5 may be the same as or different from the others, and each
is independently selected from among hydrogen, C.sub.1-C.sub.6
alkyl, C.sub.1-C.sub.6 alkenyl, C.sub.6-C.sub.10 aryl,
C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6
amino, hydrazino of the formula R.sub.aR.sub.bNNR.sub.c-- wherein
each of R.sub.a, R.sub.b and R.sub.c may be the same as or
different from one another and each is independently selected from
among C.sub.1-C.sub.6 alkyl, and pendant ligands including
functional group(s) providing further coordination to the metal
center, such as, for example, aminoalkyl, alkoxyalkyl,
aryloxyalkyl, imidoalkyl, and acetylalkyl, wherein suitable groups
in these classes include those of the following formulae:
##STR00033## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen and C.sub.1-C.sub.6 straight chain or branched
alkyl, C.sub.1-C.sub.6 straight chain or branched alkoxy,
C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of R.sub.5 and
R.sub.6 is the same as or different from the other, with each being
independently selected from among C.sub.1-C.sub.6 straight chain or
branched alkyl and C.sub.6-C.sub.10 aryl; n and m are each selected
independently from 0 to 4 with the proviso that m and n cannot be 0
at the same time, and x is selected from 1 to 5;
##STR00034## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same time;
CuHL.sub.n (xv) wherein n is an integer having a value of from 0 to
2 inclusive, and each L may be the same as or different from
other(s), each is a unidentate or multidentate Lewis-base ligand,
and each is independently selected from the group consisting of
phosphines, tertiary phosphines, ethers, polyethers, amines,
alkylamines, polyamines, glymes, crown ethers, crown thioethers,
cyclic polyamines (cyclenes), thioglymes, C.sub.2-C.sub.6 alkynes,
azoles, imidazoles, C.sub.2-C.sub.6 alkenes, pyridines,
bipyridines, isonitriles, carbenes and hetero-carbenes; and
##STR00035## wherein n is an integer having a value of from 0 to 2
inclusive, and each L may be the same as or different from the
other, each is a unidentate or multidentate Lewis-base ligand, and
each is independently selected from the group consisting of
phosphines, tertiary phosphines, ethers, polyethers, amines,
alkylamines, polyamines, glymes, crown ethers, crown thioethers,
cyclic polyamines (cyclenes), thioglymes, C.sub.2-C.sub.6 alkynes,
azoles, imidazoles, C.sub.2-C.sub.6 alkenes, pyridines,
bipyridines, isonitriles, carbenes and hetero-carbenes.
In another aspect, the invention relates to a copper precursor
formulation comprising a copper precursor compound of the
invention, and a solvent medium.
In a further aspect, the invention relates to a precursor vapor
composition, comprising a vapor of a copper precursor compound of
the invention.
A further aspect of the invention relates to a reagent source
package, comprising a storage and dispensing vessel containing a
copper precursor compound of the invention.
A still further aspect of the invention relates to a method of
making a copper borohydride compound, comprising a reaction step
selected from the following group of reaction steps:
##STR00036## wherein each of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and
R.sup.5 may be the same as or different from the others, and each
is independently selected from among hydrogen, C.sub.1-C.sub.6
alkyl, C.sub.2-C.sub.6 alkenyl, C.sub.6-C.sub.10 aryl,
C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6
alkylamino, hydrazino of the formula R.sub.aR.sub.bNNR.sub.c--
wherein each of R.sub.a, R.sub.b and R.sub.c may be the same as or
different from one another and each is independently selected from
among C.sub.1-C.sub.6 alkyl, and pendant ligands including
functional group(s) providing further coordination to the metal
center, such as, for example, aminoalkyl, alkoxyalkyl,
aryloxyalkyl, imidoalkyl, and acetylalkyl, wherein suitable groups
in these classes include those of the following formulae:
##STR00037## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen and C.sub.1-C.sub.6 straight chain or branched
alkyl, C.sub.1-C.sub.6 straight chain or branched alkoxy,
C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of R.sub.5 and
R.sub.6 is the same as or different from the other, with each being
independently selected from among C.sub.1-C.sub.6 straight chain or
branched alkyl and C.sub.6-C.sub.10 aryl; n and m are each selected
independently from 0 to 4 with the proviso that m and n cannot be 0
at the same time, and x is selected from 1 to 5;
##STR00038## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same time;
each L may be the same as or different from the other, each is a
unidentate or multidentate Lewis-base ligand, and each is
independently selected from the group consisting of phosphines,
tertiary phosphines, ethers, polyethers, amines, alkylamines,
polyamines, glymes, crown ethers, crown thioethers, cyclic
polyamines (cyclenes), thioglymes, C.sub.2-C.sub.6 alkynes, azoles,
imidazoles, C.sub.2-C.sub.6 alkenes, pyridines, bipyridines,
isonitriles, carbenes and hetero-carbenes; and X is halogen.
An additional aspect of the invention relates to a method of making
a cyclopentadienyl-type copper precursor, comprising carrying out a
synthesis selected from a synthetic route comprising
##STR00039## and recovering the cyclopentadienyl-type copper
precursor from a reaction volume including reactants and products
of such synthesis. Such synthesis may be carried out with the
cyclopentadienyl substituents instead of being all methyl are each
independently selected from among hydrogen, C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 alkenyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.6
alkoxy, C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6 amino,
hydrazino of the formula R.sub.aR.sub.bNNR.sub.c-- wherein each of
R.sub.a, R.sub.b and R.sub.c may be the same as or different from
one another and each is independently selected from among
C.sub.1-C.sub.6 alkyl, and pendant ligands including functional
group(s) providing further coordination to the metal center, such
as, for example, aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl,
and acetylalkyl, wherein suitable groups in these classes include
those of the following formulae:
##STR00040## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen and C.sub.1-C.sub.6 straight chain or branched
alkyl, C.sub.1-C.sub.6 straight chain or branched alkoxy,
C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of R.sub.5 and
R.sub.6 is the same as or different from the other, with each being
independently selected from among C.sub.1-C.sub.6 straight chain or
branched alkyl and C.sub.6-C.sub.10 aryl; n and m are each selected
independently from 0 to 4 with the proviso that m and n cannot be 0
at the same time, and x is selected from 1 to 5;
##STR00041## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same time;
and with L being a unidentate or multidentate Lewis-base ligand
selected from the group consisting of phosphines, tertiary
phosphines, ethers, polyethers, amines, alkylamines, polyamines,
glymes, crown ethers, crown thioethers, cyclic polyamines
(cyclenes), thioglymes, C.sub.2-C.sub.6 alkynes, azoles,
imidazoles, C.sub.2-C.sub.6 alkenes, pyridines, bipyridines,
isonitriles, carbenes and hetero-carbenes.
The invention in a further aspect relates to a method of making a
copper hydride compound, comprising carrying out a synthesis
including the following reaction:
##STR00042## wherein n is an integer having a value of from 0 to 2
inclusive, and each L may be the same as or different from
other(s), and each L is independently selected from the group
consisting of phosphines, tertiary phosphines, ethers, polyethers,
amines, alkylamines, polyamines, glymes, crown ethers, crown
thioethers, cyclic polyamines (cyclenes), thioglymes,
C.sub.2-C.sub.6 alkynes, azoles, imidazoles, C.sub.2-C.sub.6
alkenes, pyridines, bipyridines, isonitriles, carbenes and
hetero-carbenes.
Still another aspect of the invention relates to a copper precursor
compound selected from the group consisting of
(Ph.sub.3P).sub.2CuBH.sub.4, CpCu(CyNC), EtCpCu(tBuNC), and
MeCpCu(tBuNC), wherein Ph is phenyl, Cp is cyclopentadienyl, Cy is
cyclohexyl, Et is ethyl, and tBu is tertiary butyl.
As used herein, the designation of organic substituents by
reference to carbon numbers, includes ranges as well as sub-ranges
within the ranges identified by end-point carbon numbers, and such
sub-ranges may be specified, e.g., as including one of such
end-point carbon numbers in such a sub-range, or as including
carbon numbers greater than the lower end-point carbon number and
less than the upper end-point carbon number of the range, to
constitute various sub-ranges in the various specific embodiments
of the invention. Hydrocarbon groups may be branched or
unbranched.
Other aspects, features and embodiments of the invention will be
more fully apparent from the ensuing disclosure and appended
claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a simultaneous thermal analysis (STA) plot for
(Ph.sub.3P).sub.2CuBH.sub.4.
FIG. 2 is a 1H NMR plot for CpCu(CyNC).
FIG. 3 is a simultaneous thermal analysis (STA) plot for
CpCu(CyNC).
FIG. 4 is a 1H NMR plot for EtCpCu(tBuNC).
FIG. 5 is a simultaneous thermal analysis (STA) plot for
CpCu(CyNC).
FIG. 6 is an ORTEP diagram of the structure of EtCpCu(tBuNC).
FIG. 7 is a 1H NMR plot for MeCpCu(tBuNC).
FIG. 8 is a simultaneous thermal analysis (STA) plot for
MeCpCu(tBuNC).
DETAILED DESCRIPTION OF THE INVENTION, AND PREFERRED EMBODIMENTS
THEREOF
The present invention relates to copper precursors that have
utility in deposition of copper by film deposition techniques such
as chemical vapor deposition (CVD), atomic layer deposition (ALD)
and rapid vapor deposition (digital CVD). Such precursors include
various specific copper precursors that contain halogengen
substituents, as well as various other copper precursors that are
free of halogengen atoms (F, Cl, Br, I). From such precursors,
copper can be deposited on substrates, e.g., microelectronic device
substrates, at temperatures below 500.degree. C.
The precursors of the invention can be used for metallization of
integrated circuitry with copper. In specific embodiments, these
precursors can be employed to form copper thin films on barrier
layers in microelectronic device structures, such as on the lower
interconnect level in such device structures.
One class of copper precursors of the invention include is
constituted by copper borohydrides. This class of copper precursors
of the invention includes compounds having the structures set out
in Table 1 below, which are shown with an appertaining synthesis
reaction.
TABLE-US-00001 TABLE 1 Copper Borohydride Precursors ##STR00043##
##STR00044## ##STR00045## ##STR00046## ##STR00047##
##STR00048##
In the compounds and synthetic reactions shown in Table 1, X is
halogen (fluoro, chloro, bromo or iodo); each of R.sup.1, R.sup.2,
R.sup.3, R.sup.4 and R.sup.5 may be the same as or different from
the others, and each is independently selected from among hydrogen,
C.sub.1-C.sub.6 alkyl, C.sub.2-C.sub.6 alkenyl, C.sub.6-C.sub.10
aryl, C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6 alkylsilyl,
C.sub.1-C.sub.6 alkylamino, hydrazino of the formula
R.sub.aR.sub.bNNR.sub.c-- wherein each of R.sub.a, R.sub.b and
R.sub.c may be the same as or different from one another and each
is independently selected from among C.sub.1-C.sub.6 alkyl, and
pendant ligands including functional group(s) providing further
coordination to the metal center, such as, for example, aminoalkyl,
alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, wherein
suitable groups in these classes include those of the following
formulae:
##STR00049## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen and C.sub.1-C.sub.6 straight chain or branched
alkyl, C.sub.1-C.sub.6 straight chain or branched alkoxy,
C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of R.sub.5 and
R.sub.6 is the same as or different from the other, with each being
independently selected from among C.sub.1-C.sub.6 straight chain or
branched alkyl and C.sub.6-C.sub.10 aryl; n and m are each selected
independently from 0 to 4 with the proviso that m and n cannot be 0
at the same time, and x is selected from 1 to 5;
##STR00050## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same time;
each L may be the same as or different from the other, each is a
unidentate or multidentate Lewis-base ligand, and each is
independently selected from the group consisting of phosphines,
tertiary phosphines, ethers, polyethers, amines, alkylamines,
polyamines, glymes, crown ethers, crown thioethers, cyclic
polyamines (cyclenes), thioglymes, C.sub.2-C.sub.6 alkynes, azoles,
imidazoles, C.sub.2-C.sub.6 alkenes, pyridines, bipyridines,
isonitriles, carbenes and hetero-carbenes.
The class of copper precursors shown in Table 1 can be varied by
selection and synthesis of particular borohydride ligands that are
coordinated to the copper central atom, so that the resulting
precursor possesses a thermal and solution behavior that is
tailored for the specific deposition process in which the precursor
is employed.
The synthetic reactions shown in Table 1 are of an illustrative
character only, and other synthetic routes and reagents can be
employed, within the skill of the art, based on the disclosure
herein.
The copper precursors of Table 1 are usefully employed as
precursors for copper deposition using CVD, ALD or digital CVD
deposition processes, under process conditions that can readily
empirically be determined, to achieve deposited copper of a desired
character, e.g., film thickness, conformality, etc.
As a specific example of the thermal properties of an illustrative
compound within the scope of the general formula compounds of Table
1, a simultaneous thermal analysis (STA) plot for
(Ph.sub.3P).sub.2CuBH.sub.4 is shown in FIG. 1 hereof. In this
graph, the differential scanning calorimetry (DSC) curve shows
peaks at 153.8.degree. C. and 281.0.degree. C. The compound
evidenced good transport properties (the T50 value was 267.degree.
C.) and the thermogravimetric (TG) curve shows a low mass residue
(MR) of 8.55% for the 7.844 mg sample used in the thermal
properties characterization.
Another class of copper precursors of the invention include is
constituted by the copper compounds having cyclopentadienyl-type
ligands, of the formulae A, A', B, B', C, C', D, and D' shown in
Table II below.
TABLE-US-00002 TABLE II Copper Precursors Having
Cyclopentadienyl-Type Ligands A ##STR00051## A' ##STR00052## B
##STR00053## C ##STR00054## D ##STR00055## B' ##STR00056## C'
##STR00057## D' ##STR00058##
In such formulae A, A', B, B', C, C', D, and D', each of R.sup.1,
R.sup.2, R.sup.3, R.sup.4 and R.sup.5 may be the same as or
different from the others, and each is independently selected from
among hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.2-C.sub.6 alkenyl,
C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6
alkylsilyl, C.sub.1-C.sub.6 amino, hydrazino of the formula
R.sub.aR.sub.bNNR.sub.c-- wherein each of R.sub.a, R.sub.b and
R.sub.c may be the same as or different from one another and each
is independently selected from among C.sub.1-C.sub.6 alkyl, and
pendant ligands including functional group(s) providing further
coordination to the metal center, such as, for example, aminoalkyl,
alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, wherein
suitable groups in these classes include those of the following
formulae:
##STR00059## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen and C.sub.1-C.sub.6 straight chain or branched
alkyl, C.sub.1-C.sub.6 straight chain or branched alkoxy,
C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of R.sub.5 and
R.sub.6 is the same as or different from the other, with each being
independently selected from among C.sub.1-C.sub.6 straight chain or
branched alkyl and C.sub.6-C.sub.10 aryl; n and m are each selected
independently from 0 to 4 with the proviso that m and n cannot be 0
at the same time, and x is selected from 1 to 5;
##STR00060## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same time;
each L may be the same as or different from the other, each is a
unidentate or multidentate Lewis-base ligand, and each is
independently selected from the group consisting of phosphines,
tertiary phosphines, ethers, polyethers, amines, alkylamines,
polyamines, glymes, crown ethers, crown thioethers, cyclic
polyamines (cyclenes), thioglymes, C.sub.2-C.sub.6 alkynes, azoles,
imidazoles, C.sub.2-C.sub.6 alkenes, pyridines, bipyridines,
isonitriles, carbenes and hetero-carbenes.
The electron-deficient character of the cyclopentadienyl-like
ligands in the compounds of formulae B, B', C, C', D, D' due to the
presence of boron atom is advantageous in bonding to the
electron-rich copper central atom.
The class of copper precursors shown in Table 2 can be varied by
selection and synthesis of particular cyclopentadienyl-type
(Cp-type) ligands that are coordinated to the copper central atom,
so that the resulting precursor possesses a thermal and solution
behavior that is suitably tailored for the specific deposition
process in which such precursor is employed.
The copper precursors of Table 2 thus constitute a class of
compounds including: substituted cyclopentadienyl compounds A of
the formula (C.sub.5R.sup.1R.sup.2R.sup.3R.sup.4R.sup.5)CuL wherein
each of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 may be the
same as or different from the others, and each is independently
selected from among hydrogen, C.sub.1-C.sub.6 alkyl,
C.sub.2-C.sub.6 alkenyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.6
alkoxy, C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6 amino,
hydrazino of the formula R.sub.aR.sub.bNNR.sub.c-- wherein each of
R.sub.a, R.sub.b and R.sub.c may be the same as or different from
one another and each is independently selected from among
C.sub.1-C.sub.6 alkyl, and pendant ligands including functional
group(s) providing further coordination to the metal center, such
as, for example, aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl,
and acetylalkyl, wherein suitable groups in these classes include
those of the following formulae:
##STR00061## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen and C.sub.1-C.sub.6 straight chain or branched
alkyl, C.sub.1-C.sub.6 straight chain or branched alkoxy,
C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of R.sub.5 and
R.sub.6 is the same as or different from the other, with each being
independently selected from among C.sub.1-C.sub.6 straight chain or
branched alkyl and C.sub.6-C.sub.10 aryl; n and m are each selected
independently from 0 to 4 with the proviso that m and n cannot be 0
at the same time, and x is selected from 1 to 5;
##STR00062## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same time;
L is a unidentate or multidentate Lewis-base ligand selected from
among phosphines, tertiary phosphines, ethers, polyethers, amines,
alkylamines, polyamines, glymes, crown ethers, crown thioethers,
cyclic polyamines (cyclenes), thioglymes, C.sub.2-C.sub.6 alkynes,
azoles, imidazoles, C.sub.2-C.sub.6 alkenes, pyridines,
bipyridines, isonitriles, carbenes and hetero-carbenes; substituted
cyclopentadienyl compounds A' of the formula
(C.sub.5R.sup.1R.sup.2R.sup.3R.sup.4R.sup.5).sub.2Cu wherein each
of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 may be the same
as or different from the others, and each is independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6
alkenyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.6 alkoxy,
C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6 amino, hydrazino of the
formula R.sub.aR.sub.bNNR.sub.c-- wherein each of R.sub.a, R.sub.b
and R.sub.c may be the same as or different from one another and
each is independently selected from among C.sub.1-C.sub.6 alkyl,
and pendant ligands including functional group(s) providing further
coordination to the metal center, such as, for example, aminoalkyl,
alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, wherein
suitable groups in these classes include those of the following
formulae:
##STR00063## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen and C.sub.1-C.sub.6 straight chain or branched
alkyl, C.sub.1-C.sub.6 straight chain or branched alkoxy,
C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of R.sub.5 and
R.sub.6 is the same as or different from the other, with each being
independently selected from among C.sub.1-C.sub.6 straight chain or
branched alkyl and C.sub.6-C.sub.10 aryl; n and m are each selected
independently from 0 to 4 with the proviso that m and n cannot be 0
at the same time, and x is selected from 1 to 5;
##STR00064## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same time;
thiaborolyl compounds B of the formula
(C.sub.3BSR.sup.1R.sup.2R.sup.3R.sup.5)CuL wherein each of R.sup.1,
R.sup.2, R.sup.3, R.sup.4 and R.sup.5 may be the same as or
different from the others, and each is independently selected from
among hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkenyl,
C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6
alkylsilyl, C.sub.1-C.sub.6 amino, hydrazino of the formula
R.sub.aR.sub.bNNR.sub.c-- wherein each of R.sub.a, R.sub.b and
R.sub.c may be the same as or different from one another and each
is independently selected from among C.sub.1-C.sub.6 alkyl, and
pendant ligands including functional group(s) providing further
coordination to the metal center, such as, for example, aminoalkyl,
alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, wherein
suitable groups in these classes include those of the following
formulae:
##STR00065## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen and C.sub.1-C.sub.6 straight chain or branched
alkyl, C.sub.1-C.sub.6 straight chain or branched alkoxy,
C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of R.sub.5 and
R.sub.6 is the same as or different from the other, with each being
independently selected from among C.sub.1-C.sub.6 straight chain or
branched alkyl and C.sub.6-C.sub.10 aryl; n and m are each selected
independently from 0 to 4 with the proviso that m and n cannot be 0
at the same time, and x is selected from 1 to 5;
##STR00066## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same time;
and L is a unidentate or multidentate Lewis-base ligand selected
from among phosphines, tertiary phosphines, ethers, polyethers,
amines, alkylamines, polyamines, glymes, crown ethers, crown
thioethers, cyclic polyamines (cyclenes), thioglymes,
C.sub.2-C.sub.6 alkynes, azoles, imidazoles, C.sub.2-C.sub.6
alkenes, pyridines, bipyridines, isonitriles, carbenes and
hetero-carbenes; thiaborolyl compounds B' of the formula
(C.sub.3BSR.sup.1R.sup.2R.sup.3R.sup.5).sub.2Cu wherein each of
R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 may be the same as
or different from the others, and each is independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6
alkenyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.6 alkoxy,
C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6 amino, hydrazino of the
formula R.sub.aR.sub.bNNR.sub.c-- wherein each of R.sub.a, R.sub.b
and R.sub.c may be the same as or different from one another and
each is independently selected from among C.sub.1-C.sub.6 alkyl,
and pendant ligands including functional group(s) providing further
coordination to the metal center, such as, for example, aminoalkyl,
alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, wherein
suitable groups in these classes include those of the following
formulae:
##STR00067## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen and C.sub.1-C.sub.6 straight chain or branched
alkyl, C.sub.1-C.sub.6 straight chain or branched alkoxy,
C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of R.sub.5 and
R.sub.6 is the same as or different from the other, with each being
independently selected from among C.sub.1-C.sub.6 straight chain or
branched alkyl and C.sub.6-C.sub.10 aryl; n and m are each selected
independently from 0 to 4 with the proviso that m and n cannot be 0
at the same time, and x is selected from 1 to 5;
##STR00068## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same time;
azaborolyl compounds C of the formula
(C.sub.3BNR.sup.1R.sup.2R.sup.3R.sup.4R.sup.5)CuL wherein each of
R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 may be the same as
or different from the others, and each is independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.2-C.sub.6
alkenyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.6 alkoxy,
C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6 amino, hydrazino of the
formula R.sub.aR.sub.bNNR.sub.c-- wherein each of R.sub.a, R.sub.b
and R.sub.c may be the same as or different from one another and
each is independently selected from among C.sub.1-C.sub.6 alkyl,
and pendant ligands including functional group(s) providing further
coordination to the metal center, such as, for example, aminoalkyl,
alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, wherein
suitable groups in these classes include those of the following
formulae:
##STR00069## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen and C.sub.1-C.sub.6 straight chain or branched
alkyl, C.sub.1-C.sub.6 straight chain or branched alkoxy,
C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of R.sub.5 and
R.sub.6 is the same as or different from the other, with each being
independently selected from among C.sub.1-C.sub.6 straight chain or
branched alkyl and C.sub.6-C.sub.10 aryl; n and m are each selected
independently from 0 to 4 with the proviso that m and n cannot be 0
at the same time, and x is selected from 1 to 5;
##STR00070## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same time;
L is a unidentate or multidentate Lewis-base ligand selected from
among phosphines, tertiary phosphines, ethers, polyethers, amines,
alkylamines, polyamines, glymes, crown ethers, crown thioethers,
cyclic polyamines (cyclenes), thioglymes, C.sub.2-C.sub.6 alkynes,
azoles, imidazoles, C.sub.2-C.sub.6 alkenes, pyridines,
bipyridines, isonitriles, carbenes and hetero-carbenes; azaborolyl
compounds C' of the formula
(C.sub.3BNR.sup.1R.sup.2R.sup.3R.sup.4R.sup.5).sub.2Cu wherein each
of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 may be the same
as or different from the others, and each is independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.2-C.sub.6
alkenyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.6 alkoxy,
C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6 amino, hydrazino of the
formula R.sub.aR.sub.bNNR.sub.c-- wherein each of R.sub.a, R.sub.b
and R.sub.c may be the same as or different from one another and
each is independently selected from among C.sub.1-C.sub.6 alkyl,
and pendant ligands including functional group(s) providing further
coordination to the metal center, such as, for example, aminoalkyl,
alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, wherein
suitable groups in these classes include those of the following
formulae:
##STR00071## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen and C.sub.1-C.sub.6 straight chain or branched
alkyl, C.sub.1-C.sub.6 straight chain or branched alkoxy,
C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of R.sub.5 and
R.sub.6 is the same as or different from the other, with each being
independently selected from among C.sub.1-C.sub.6 straight chain or
branched alkyl and C.sub.6-C.sub.10 aryl; n and m are each selected
independently from 0 to 4 with the proviso that m and n cannot be 0
at the same time, and x is selected from 1 to 5;
##STR00072## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same time;
oxoborolyl compounds D of the formula
(C.sub.3BOR.sup.1R.sup.2R.sup.3R.sup.5)CuL wherein each of R.sup.1,
R.sup.2, R.sup.3, R.sup.4 and R.sup.5 may be the same as or
different from the others, and each is independently selected from
among hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.2-C.sub.6 alkenyl,
C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6
alkylsilyl, C.sub.1-C.sub.6 amino, hydrazino of the formula
R.sub.aR.sub.bNNR.sub.c-- wherein each of R.sub.a, R.sub.b and
R.sub.c may be the same as or different from one another and each
is independently selected from among C.sub.1-C.sub.6 alkyl, and
pendant ligands including functional group(s) providing further
coordination to the metal center, such as, for example, aminoalkyl,
alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, wherein
suitable groups in these classes include those of the following
formulae:
##STR00073## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen and C.sub.1-C.sub.6 straight chain or branched
alkyl, C.sub.1-C.sub.6 straight chain or branched alkoxy,
C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of R.sub.5 and
R.sub.6 is the same as or different from the other, with each being
independently selected from among C.sub.1-C.sub.6 straight chain or
branched alkyl and C.sub.6-C.sub.10 aryl; n and m are each selected
independently from 0 to 4 with the proviso that m and n cannot be 0
at the same time, and x is selected from 1 to 5;
##STR00074## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same time;
L is a unidentate or multidentate Lewis-base ligand selected from
among phosphines, tertiary phosphines, ethers, polyethers, amines,
alkylamines, polyamines, glymes, crown ethers, crown thioethers,
cyclic polyamines (cyclenes), thioglymes, C.sub.2-C.sub.6 alkynes,
azoles, imidazoles, C.sub.2-C.sub.6 alkenes, pyridines,
bipyridines, isonitriles, carbenes and hetero-carbenes; and
oxoborolyl compounds D' of the formula
(C.sub.3BOR.sup.1R.sup.2R.sup.3R.sup.5).sub.2Cu wherein each of
R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 may be the same as
or different from the others, and each is independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.2-C.sub.6
alkenyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.6 alkoxy,
C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6 amino, hydrazino of the
formula R.sub.aR.sub.bNNR.sub.c-- wherein each of R.sup.a, R.sub.b
and R.sub.c may be the same as or different from one another and
each is independently selected from among C.sub.1-C.sub.6 alkyl,
and pendant ligands including functional group(s) providing further
coordination to the metal center, such as, for example, aminoalkyl,
alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, wherein
suitable groups in these classes include those of the following
formulae:
##STR00075## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen and C.sub.1-C.sub.6 straight chain or branched
alkyl, C.sub.1-C.sub.6 straight chain or branched alkoxy,
C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of R.sub.5 and
R.sub.6 is the same as or different from the other, with each being
independently selected from among C.sub.1-C.sub.6 straight chain or
branched alkyl and C.sub.6-C.sub.10 aryl; n and m are each selected
independently from 0 to 4 with the proviso that m and n cannot be 0
at the same time, and x is selected from 1 to 5;
##STR00076## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same
time.
The foregoing copper precursors of formulae A, A', B, B', C, C', D,
and D' are usefully employed as precursors for copper deposition
using CVD, ALD or digital CVD deposition processes, under process
conditions that can readily empirically be determined, to achieve
deposited copper of a desired character, e.g., film thickness,
conformality, etc.
Set out in Table 3 below is an illustrative synthesis scheme for
compounds of formulae A and A'.
TABLE-US-00003 TABLE 3 Synthetic Route for Formula A and A' Copper
Precursors ##STR00077##
wherein L is selected from among phosphines, tertiary phosphines,
ethers, polyethers, amines, alkylamines, polyamines, glymes, crown
ethers, crown thioethers, cyclic polyamines (cyclenes), thioglymes,
C.sub.2-C.sub.6 alkynes, azoles, imidazoles, C.sub.2-C.sub.6
alkenes, pyridines, bipyridines, isonitriles, carbenes and
hetero-carbenes, and wherein such synthesis may be carried out with
the cyclopentadienyl substituents instead of being all methyl are
each independently selected from among hydrogen, C.sub.1-C.sub.6
alkyl, C.sub.1-C.sub.6 alkenyl, C.sub.6-C.sub.10 aryl,
C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6 alkylsilyl, C.sub.1-C.sub.6
amino, hydrazino of the formula R.sub.aR.sub.bNNR.sub.c-- wherein
each of R.sub.a, R.sub.b and R.sub.c may be the same as or
different from one another and each is independently selected from
among C.sub.1-C.sub.6 alkyl, and pendant ligands including
functional group(s) providing further coordination to the metal
center, such as, for example, aminoalkyl, alkoxyalkyl,
aryloxyalkyl, imidoalkyl, and acetylalkyl, wherein suitable groups
in these classes include those of the following formulae:
##STR00078## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen and C.sub.1-C.sub.6 straight chain or branched
alkyl, C.sub.1-C.sub.6 straight chain or branched alkoxy,
C.sub.6-C.sub.10 aryl and NR.sub.5R.sub.6; each of R.sub.5 and
R.sub.6 is the same as or different from the other, with each being
independently selected from among C.sub.1-C.sub.6 straight chain or
branched alkyl and C.sub.6-C.sub.10 aryl; n and m are each selected
independently from 0 to 4 with the proviso that m and n cannot be 0
at the same time, and x is selected from 1 to 5;
##STR00079## wherein each of R.sub.1-R.sub.4 is the same as or
different from one another, with each being independently selected
from among hydrogen, C.sub.1-C.sub.6 alkyl, and C.sub.6-C.sub.10
aryl; R.sub.5 is selected from among C.sub.1-C.sub.6 alkyl, and
C.sub.6-C.sub.10 aryl; and n and m are selected independently from
0 to 4, with the proviso that m and n cannot be 0 at the same
time.
The synthetic reactions shown in Table 3 are of an illustrative
character only, and other synthetic routes and reagents can be
employed, within the skill of the art, based on the disclosure
herein.
A further class of copper precursors of the invention comprises
substituted cyclopentadienyl compounds of formula E:
##STR00080## wherein each of R.sup.1, R.sup.2, R.sup.3, R.sup.4 and
R.sup.5 may be the same as or different from the others, and each
is independently selected from among hydrogen, halogengen,
C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy and cyanide (--CN),
and L is selected from among phosphines, tertiary phosphines,
ethers, polyethers, amines, alkylamines, polyamines, glymes, crown
ethers, crown thioethers, cyclic polyamines (cyclenes), thioglymes,
C.sub.2-C.sub.6 alkynes, azoles, imidazoles, C.sub.2-C.sub.6
alkenes, pyridines, bipyridines, isonitriles, carbenes and
hetero-carbenes.
These formula E compounds,
(C.sub.5R.sup.1R.sup.2R.sup.3R.sup.4R.sup.5)CuL, can be readily
synthesized by an alternative synthetic techniques to those
discussed above in connection with the compounds of Table 2 and
illustrative synthesis route of Table 3 starting with Cu.sub.2O and
monomeric cyclopendienes.
Illustrative compounds of formula E include MeCpCu(tBuNC),
EtCpCu(tBuNC), and CpCu(CyNC), wherein Me is methyl, Cp is
cyclopentadienyl, tBu is tert-butyl, Et is ethyl and Cy is
isocyanato. Characterization data for these formula E compounds are
set out in FIGS. 2-7, by way of example.
FIG. 2 is a 1H NMR plot for CpCu(CyNC).
FIG. 3 is a simultaneous thermal analysis (STA) plot for
CpCu(CyNC). In this graph, the differential scanning calorimetry
(DSC) curve shows peaks in the vicinity of 90.degree. C. and
190.degree. C. The thermogravimetric (TG) curve shows a mass
residue (MR) of 37% for the 9.90 mg sample used in the thermal
properties characterization.
FIG. 4 is a 1H NMR plot for EtCpCu(tBuNC).
FIG. 5 is a simultaneous thermal analysis (STA) plot for
CpCu(CyNC). In this graph, the differential scanning calorimetry
(DSC) curve shows peaks in the vicinity of 55.degree. C.,
160.degree. C. and 210.degree. C. The thermogravimetric (TG) curve
shows a mass residue (MR) of 28% for the 11.01 mg sample used in
the thermal properties characterization.
FIG. 6 is an ORTEP diagram of the structure of EtCpCu(tBuNC).
FIG. 7 is a 1H NMR plot for MeCpCu(tBuNC).
FIG. 8 is a simultaneous thermal analysis (STA) plot for
MeCpCu(tBuNC). In this graph, the differential scanning calorimetry
(DSC) curve shows peaks in the vicinity of 120.degree. C.,
175.degree. C. and 210.degree. C. The thermogravimetric (TG) curve
shows a mass residue (MR) of 31% for the 12.42 mg sample used in
the thermal properties characterization.
Yet another class of copper precursors of the invention is
constituted by copper hydride compounds of the formula CuHLn
wherein n is an integer having a value of from 0 to 2 inclusive,
and each L may be the same as or different from the other, each is
a unidentate or multidentate Lewis-base ligand, and each L is
independently selected from the group consisting of phosphines,
tertiary phosphines, ethers, polyethers, amines, alkylamines,
polyamines, glymes, crown ethers, crown thioethers, cyclic
polyamines (cyclenes), thioglymes, C.sub.2-C.sub.6 alkynes, azoles,
imidazoles, C.sub.2-C.sub.6 alkenes, pyridines, bipyridines,
isonitriles, carbenes and hetero-carbenes, and n is an integer
having a value of from 0 to 2 inclusive.
Such copper hydride precursors are capable of forming trimers of
the formula
##STR00081## wherein each L is independently selected from the
group consisting of phosphines, tertiary phosphines, ethers,
polyethers, amines, alkylamines, polyamines, glymes, crown ethers,
crown thioethers, cyclic polyamines (cyclenes), thioglymes,
C.sub.2-C.sub.6 alkynes, azoles, imidazoles, C.sub.2-C.sub.6
alkenes, pyridines, bipyridines, isonitriles, carbenes and
hetero-carbenes, and n is an integer having a value of from 0 to 2
inclusive.
These copper hydride monomer and trimer precursors of the invention
have utility for copper deposition processes such as CVD, ALD and
digital CVD, and may be utilized in solid or liquid forms that are
volatilized to form corresponding precursor vapor that is contacted
with the microelectronic device substrate or other suitable
deposition surface to effect deposition of copper thereon.
Such copper hydride precursors in their respective monomer and
trimer forms can be varied by selection and synthesis of particular
ligands L that are coordinated to the copper central atom, so that
the resulting precursor possesses a thermal and solution behavior
that is suitably tailored for the specific deposition process in
which such precursor is employed. The ligands in specific
embodiments may for example be selected to provide the copper
precursor with an environmentally benign or readily biodegradable
character. In various embodiments of the invention, the ligand L is
selected from among tertiary phosphines, azoles, imidazoles,
pyridines, and bipyridines.
The copper hydride precursors described above can be synthesized in
any suitable manner. In one embodiment, the aforementioned trimer
copper precursors are formed by the following synthesis
reaction:
##STR00082## wherein each L is independently selected from the
group consisting of phosphines, tertiary phosphines, ethers,
polyethers, amines, alkylamines, polyamines, glymes, crown ethers,
crown thioethers, cyclic polyamines (cyclenes), thioglymes,
C.sub.2-C.sub.6 alkynes, azoles, imidazoles, C.sub.2-C.sub.6
alkenes, pyridines, bipyridines, isonitriles, carbenes and
hetero-carbenes, and n is an integer having a value of from 0 to 2
inclusive.
The copper precursors of the invention, as variously described
herein, are usefully employed for deposition of conformal copper or
copper-containing films using CVD/ALD/digital CVD techniques, as
monomeric copper precursors that are transportable (volatile) at
temperatures specific to such processes, e.g., temperatures below
500.degree. C. The copper precursors of the invention can be
readily synthesized from the parent ligands and the metal, to
provide such precursors in readily recoverable form.
The copper precursors of the invention may be packaged in a
precursor storage and dispensing package of any suitable type.
Depending on the form, e.g., solid or liquid form, of the
precursor, suitable storage and dispensing packages may include
those described in U.S. Provisional Patent Application No.
60/662,515 filed in the names of Paul J. Marganski, et al. for
"SYSTEM FOR DELIVERY OF REAGENTS FROM SOLID SOURCES THEREOF" and
the storage and dispensing apparatus variously described in U.S.
Pat. No. 5,518,528; U.S. Pat. No. 5,704,965; U.S. Pat. No.
5,704,967; U.S. Pat. No. 5,707,424; U.S. Pat. No. 6,101,816; U.S.
Pat. No. 6,089,027; U.S. Pat. No. 7,172,646; U.S. Pat. No.
6,921,062; U.S. Pat. No. 7,300,038; and U.S. Patent application
Pub. No. 2003-0111014, the disclosures of all of which are hereby
incorporated herein by reference, in their respective
entireties.
In CVD, ALD or digital CVD usage, the copper precursors of the
invention are volatilized to form a precursor vapor that is then
contacted with a microelectronic device substrate under elevated
temperature vapor decomposition conditions to deposit copper on the
substrate.
CVD involves the contacting of a volatile metal-organic compound in
the gas phase with areas of a substrate where growth of a metal
film (e.g., to form an interconnect) is required. A surface
catalyzed chemical reaction, e.g., thermal decomposition, occurs
and produces deposition of the desired metal. Since the metal film
steadily grows on the desired surface, it is of a uniform thickness
and highly conformal even to severe (e.g., high aspect) geometries.
CVD is well suited to use in fabricating submicron high aspect
ratio features. The copper precursors of the invention are
well-suited for such CVD usage.
ALD involves the deposition of successive monolayer over a
substrate within a deposition chamber typically maintained at
subatmospheric pressure. An exemplary method includes feeding a
single vaporized precursor into a deposition chamber to form a
first monolayer over a substrate positioned therein. The substrate
is heated to a temperature that is high enough to prevent
condensation of the precursor but low enough to prevent thermal
decomposition of said precursor. Thereafter, the flow of the first
deposition precursor is ceased and an inert purge gas, e.g.,
nitrogen or argon, is flowed through the chamber to exhaust any
unreacted first precursor from the chamber. Subsequently, a second
vaporized precursor the same as or different from the first is
flowed into the chamber to form a second monolayer upon the first
monolayer. The second monolayer might react with the first
monolayer. Additional precursors can form successive monolayer, or
the above process can be repeated until a desired thickness and
composition layer has been formed over the substrate. The copper
precursors of the invention are well-suited for ALD processes.
Digital CVD involves the alternate introduction of reactant gases
over a surface of a substrate, and is similar to ALD, but digital
CVD accommodates a more rapid growth of the deposited film. In
general, digital CVD achieves a rapid film growth similar to that
obtained by CVD techniques, but with a high conformality of the
deposited film that is characteristic of ALD techniques. The copper
precursors of the invention are well-suited for digital CVD
processes.
The copper precursors of the present invention are volatile and
thermally stable, and are usefully employed as solid copper CVD or
ALD precursors under reduced pressure deposition conditions in the
CVD or ALD reactor. Alternatively, the solid precursors can be
dissolved in organic solvents, and liquid delivery processes can be
used to meter the solution into a vaporizer for transport of the
vapor to the reactor.
The copper precursor compositions of the present invention may be
used to form copper interconnect lines in microelectronic device
integrated circuitry, thin-film circuitry, thin-film packaging
components and thin-film recording head coils. To fabricate such
integrated circuitry or thin-film circuitry, a microelectronic
device substrate may be utilized having a number of dielectric and
conductive layers (multilayers) formed on and/or within the
substrate. The microelectronic device substrate may include a bare
substrate or any number of constituent layers formed on a bare
substrate. As defined herein, "microelectronic device" corresponds
to semiconductor substrates, flat panel displays, and
microelectromechanical systems (MEMS).
In the broad practice of the present invention, a copper-containing
layer may be formed on a microelectronic device substrate using the
copper precursor, for use in a first, second, third, or more
metallization layer. Such copper layers typically are used in
circuit locations requiring low resistivity, high performance
and/or high speed circuit paths. A barrier layer may be deposited
or otherwise formed on the microelectronic device substrate before
a copper layer is formed on said substrate.
Using the copper precursor compositions described herein, copper
can be deposited on wafer substrates using CVD, ALD or digital CVD
systems, such systems being well known in the microelectronic
device fabrication art. Further, water, water-generating compounds,
or other adjuvants to the precursor formulation may be mixed with
the copper precursor upstream of, at, or within, the CVD, ALD or
digital CVD tool. Reducing agents may be utilized in an analogous
fashion.
As a further variation, when copper alloy compositions are to be
deposited on the substrate, the copper precursor formulation may
contain or be mixed with other metal source reagent materials, or
such other reagent materials may be separately vaporized and
introduced to the deposition chamber.
The compositions of the present invention may be delivered to a
CVD, ALD or digital CVD reactor in a variety of ways. For example,
a liquid delivery system may be utilized. Alternatively, a combined
liquid delivery and flash vaporization process unit may be
employed, such as the LDS300 liquid delivery and vaporizer unit
(commercially available from ATMI, Inc., Danbury, Conn., USA), to
enable low volatility materials to be volumetrically delivered,
leading to reproducible transport and deposition without thermal
decomposition of the precursor. Both of these considerations of
reproducible transport and deposition without thermal decomposition
are essential for providing a commercially acceptable copper CVD,
ALD or digital CVD process.
In liquid delivery formulations, copper precursors that are liquids
may be used in neat liquid form, or liquid or solid copper
precursors may be employed in solvent formulations containing same.
Thus, copper precursor formulations of the invention may include
solvent component(s) of suitable character as may be desirable and
advantageous in a given end use application to form copper on a
substrate.
Suitable solvents may for example include alkane solvents (e.g.,
hexane, heptane, octane, and pentane), aryl solvents (e.g., benzene
or toluene), amines (e.g., triethylamine, tert-butylamine), imines
and carbodiimides (e.g., N,N'-diisopropylcarbodiimide), alcohols,
ethers, ketones, aldehydes, amidines, guanadines, isoureas, and the
like. The utility of specific solvent compositions for particular
copper precursors may be readily empirically determined, to select
an appropriate single component or multiple component solvent
medium for the liquid delivery vaporization and transport of the
specific copper precursor that is employed.
A wide variety of CVD, ALD or digital CVD process conditions may be
employed in the use of the precursor compositions of the present
invention. Generalized process conditions may include substrate
temperature in a range of 50-400.degree. C.; pressure in a range of
0.05-50 Torr; and carrier gas flows of helium, hydrogen, nitrogen,
or argon in a range of 25-750 sccm, at a temperature approximately
the same as the vaporizer, e.g., in a range of 50 to 120.degree.
C.
The deposition of copper thin films with useful electrical
properties (low resistivity) and good adhesion to the barrier layer
(e.g., formed of TiN or TaN), are also achieved by the process and
precursors of the present invention. The conformality of the
deposited film is practically achievable through CVD, ALD or
digital CVD techniques that preferably provide a pathway to the
achievement of "full-fill" copper metallization. The liquid
delivery approach of the present invention, including "flash"
vaporization and the use of copper precursor chemistry as herein
disclosed, enable next-generation device geometries and dimensions
to be attained, e.g., a conformal vertical interconnect of 22
nanometer line width. The conformal deposition of interconnects of
these critical dimensions cannot be realized by currently available
physical deposition methods. Thus, the approach of the present
invention affords a viable pathway to future generation devices,
and embodies a substantial advance in the art.
The features and advantages of the invention are more fully shown
by the following illustrative and non-limiting examples.
Example 1
Synthesis of (Ethyl-tetrahapto-cyclopendienyl)(tert-butyl
isocyanide) Copper (I) ((EtC.sub.p)Cu(Bu.sup.tNC))
A mixture of 5.0 g (34.9 mmol) of Cu.sub.2O, 5.0 g (60.1 mmol)
Bu.sup.tNC and 23.5 g (250 mmol) of freshly cracked EtCpH was mixed
at room temperature and then heated at 100.degree. C. for an hour.
After the mixture was cooled down to room temperature, 100 mL ethyl
ether was added before the filtration. After the filtration, the
resulting filtrate was dark yellow. Recrystallization in pentane
gave 4.2 g dark yellow crude solid (EtCp)Cu(Bu.sup.tNC) was
obtained. (17.5 mmol, 29% overall yield based on Bu.sup.tNC). Data
for (EtCp)Cu(Bu.sup.tNC): .sup.1H NMR (benzene-d.sub.6, 21.degree.
C.) (FIG. 1.1): .delta. 0.56 (t, 9H, --C(CH.sub.3).sub.3), 1.42 (t,
3H, --CH.sub.2CH.sub.3), 2.24 (q, 2H, --CH.sub.2CH.sub.3), 6.17 (s,
5H, --C.sub.5H.sub.5). Anal. CuNC.sub.12H.sub.18: Calcd. C, 60.10%;
H, 7.57%; N, 5.84%. Found: C, 59.95%; H, 7.58%; N, 5.67%.
Example 2
Synthesis of (Methyl-tetrahapto-cyclopendienyl)(tert-butyl
isocyanide) Copper (I) ((MeC.sub.p)Cu(Bu.sup.tNC))
A mixture of 5.0 g (34.9 mmol) of Cu.sub.2O, 5.0 g (60.1 mmol)
Bu.sup.tNC and 20.0 g (250 mmol) of freshly cracked MeCpH was mixed
at room temperature and then heated at 100.degree. C. for an hour.
After the mixture was cooled down to room temperature, 100 mL ethyl
ether was added before the filtration. After the filtration, the
resulting filtrate was dark yellow. Recrystallization in pentane
gave 3.8 g dark yellow crude solid (MeCp)Cu(Bu.sup.tNC) was
obtained. (16.8 mmol, 28% overall yield based on Bu.sup.tNC). Data
for (MeCp)Cu(Bu.sup.tNC): .sup.1H NMR (benzene-d.sub.6, 21.degree.
C.) (FIG. 1.4): .delta. 0.55 (t, 9H, --C(CH.sub.3).sub.3), 2.50 (s,
3H, --CH.sub.3), 6.17 (s, 5H, --C.sub.5H.sub.5). Anal.
CuNC.sub.11H.sub.16 Calcd. C, 58.51%; H, 7.14%; N, 6.20%. Found: C,
58.67%; H, 7.13%; N, 5.95%.
Example 3
Synthesis of (Methyl-tetrahapto-cyclopendienyl)(cyclohexyl
isocyanide) Copper (I) C.sub.pCu(CyNC))
A mixture of 3.81 g (26.6 mmol) of Cu.sub.2O, 5.0 g (34.9 mmol)
CyNC and 12.56 g (157 mmol) of freshly cracked CpH was mixed at
room temperature and then heated at 100.degree. C. for an hour.
After the mixture was cooled down to room temperature, 100 mL ethyl
ether was added before the filtration. After the filtration, the
resulting filtrate was dark yellow. Recrystallization in pentane
gave 5.5 g dark yellow solid CpCu(CyNC) was obtained after
sublimation at 120.degree. C. under 200 mtorr vacuum. (23.0 mmol,
66% overall yield based on CyNC). Data for CpCu(CyNC): .sup.1H NMR
(benzene-d.sub.6, 21.degree. C.) (FIG. 1.6): .delta. 0.61, 0.85,
0.93, 1.08 and 2.50 (m, 11H, C.sub.6H.sub.11), 2.50 (s, 3H,
--CH.sub.3), 6.31 (s, 5H, --C.sub.5H.sub.5). Anal.
CuNC.sub.12H.sub.17: Calcd. C, 60.35%; H, 7.17%; N, 5.87%. Found:
C, 60.50%; H, 6.96%; N, 5.95%.
Example 4
Synthesis of (pentahapto-cyclopendienyl)(tert-butyl isocyanide)
Copper (I) ((C.sub.pCu(Bu.sup.tNC))
A mixture of 5.0 g (34.9 mmol) of Cu.sub.2O, 5.0 g (60.1 mmol)
Bu.sup.tNC and 16.5 g (250 mmol) of freshly cracked CpH was mixed
at room temperature and then heated at 70.degree. C. for an hour.
After the mixture was cooled down to room temperature, 50 mL ethyl
ether was added before the filtration. After the filtration, the
resulting filtrate was dark yellow. All the volatiles were pulled
away in vacuo and 10 g dark yellow crude solid CpCu(Bu.sup.tNC) was
obtained. Sublimation at 100.degree. C. under 200 mtorr yielded 6 g
pale yellow solid (28.3 mmol, 47% overall yield based on
Bu.sup.tNC). Data for CpCu(Bu.sup.tNC): .sup.1H NMR
(benzene-d.sub.6, 21.degree. C.) (FIG. 1.1): .delta. 0.53 (t, 9H,
--C(CH.sub.3).sub.3), 6.34 (s, 5H, --C.sub.5H.sub.5). Anal.
CuNC.sub.10H.sub.14: Calcd. C, 56.72%; H, 6.66%; N, 6.61%. Found:
C, 56.59%; H, 6.75%; N, 6.69%.
The advantages and features of the invention are further
illustrated with reference to the following example, which is not
to be construed as in any way limiting the scope of the invention
but rather as illustrative of one embodiment of the invention in a
specific application thereof.
While the invention has been has been described herein in reference
to specific aspects, features and illustrative embodiments of the
invention, it will be appreciated that the utility of the invention
is not thus limited, but rather extends to and encompasses numerous
other variations, modifications and alternative embodiments, as
will suggest themselves to those of ordinary skill in the field of
the present invention, based on the disclosure herein.
Correspondingly, the invention as hereinafter claimed is intended
to be broadly construed and interpreted, as including all such
variations, modifications and alternative embodiments, within its
spirit and scope.
* * * * *